CN112441930A - Compound, light-emitting device, light-emitting apparatus, electronic device, and lighting apparatus - Google Patents

Compound, light-emitting device, light-emitting apparatus, electronic device, and lighting apparatus Download PDF

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CN112441930A
CN112441930A CN202010898337.4A CN202010898337A CN112441930A CN 112441930 A CN112441930 A CN 112441930A CN 202010898337 A CN202010898337 A CN 202010898337A CN 112441930 A CN112441930 A CN 112441930A
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light
compound
carbon atoms
emitting device
substituted
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春山拓哉
濑尾哲史
大泽信晴
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Abstract

The invention relates to a compound, a light-emitting device, a light-emitting apparatus, an electronic apparatus, and a lighting apparatus. Provided is a novel compound represented by the following general formula (G1).
Figure 1
In the above general formula (G1), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused aromatic ringA fused heteroaromatic ring having 10 to 30 carbon atoms, R1Represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms. Furthermore, Y1And Y2Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms.

Description

Compound, light-emitting device, light-emitting apparatus, electronic device, and lighting apparatus
Technical Field
One embodiment of the present invention relates to a compound, a light-emitting device, an electronic device, and a lighting device. However, one embodiment of the present invention is not limited to the above-described technical field. That is, one embodiment of the present invention relates to an object, a method, a manufacturing method, or a driving method. In addition, one embodiment of the present invention relates to a process (process), a machine (machine), a product (manufacture), or a composition (machine).
Background
In recent years, research and development of light emitting devices using Electroluminescence (EL) have been increasingly hot. A light-emitting device has a structure in which an EL layer (containing a light-emitting substance) is interposed between a pair of electrodes. When a voltage is applied between a pair of electrodes, electrons and holes injected from the respective electrodes are recombined in the EL layer, so that a light-emitting substance (organic compound) included in the EL layer is in an excited state, and light is emitted when the excited state returns to a ground state. Further, as the kind of excited state, a singlet excited state (S) may be mentioned*) And triplet excited state (T)*) In this case, light emission from a singlet excited state is referred to as fluorescence, and light emission from a triplet excited state is referred to as phosphorescence. Further, in the light-emitting device, the statistical generation ratio of the singlet excited state and the triplet excited state is considered to be S*∶T*1: 3. Therefore, the efficiency of a light-emitting device including a phosphorescent substance capable of converting energy of a triplet excited state into light emission is improved, and the light-emitting device has been actively developed in recent years.
As a material capable of converting part or all of triplet excitation energy into luminescence, a Thermally Activated Delayed Fluorescence (TADF) material is known in addition to a phosphorescent substance. In the TADF material, a singlet excited state can be generated from a triplet excited state by intersystem crossing.
Further, the following methods are also known: in a light-emitting device including a TADF material and a fluorescent substance, singlet excitation energy of the TADF material is transferred to the fluorescent substance, so that the fluorescent substance emits light with high efficiency (see patent document 1).
In order to increase the energy transfer efficiency (increase the energy transfer rate) by the forster mechanism, it is generally preferable to increase the concentration ratio of the guest material (fluorescent substance) to the host material in the light-emitting layer of the light-emitting device. However, when the concentration ratio of the guest material is increased, the energy transfer speed based on the dexter mechanism also becomes faster, which leads to a decrease in the luminous efficiency, i.e., in the depthwise relationship. Therefore, increasing the concentration ratio of the guest material is not effective for improving the light emission efficiency.
[ patent document 1] Japanese patent application laid-open No. 2014-45179
Disclosure of Invention
It is an object of one embodiment of the present invention to provide a novel compound. Further, an object of one embodiment of the present invention is to provide a light-emitting device capable of efficiently receiving a singlet excited state (S) from a host material even when a concentration ratio in an EL layer of the light-emitting device is increased *) Is not easily excited from the triplet excited state (T) of the host material (hereinafter referred to as singlet excitation energy)*) A novel compound which generates energy transfer (hereinafter referred to as triplet excitation energy) (which can suppress energy transfer based on the dexter mechanism).
Further, an object of one embodiment of the present invention is to provide a novel compound which can be used for a light-emitting device. Further, an object of one embodiment of the present invention is to provide a novel compound which can be used for an EL layer of a light-emitting device. Another object of one embodiment of the present invention is to provide a novel light-emitting device with high emission efficiency using the novel compound of one embodiment of the present invention. Another object of one embodiment of the present invention is to provide a novel light-emitting device, a novel electronic device, or a novel lighting device.
Note that the description of the above object does not hinder the existence of other objects. It is not necessary for one embodiment of the invention to achieve all of the above objectives. Further, objects other than the above objects can be found and derived from the description of the specification, the drawings, the claims, and the like.
One embodiment of the present invention is a fluorescent substance, which is a compound represented by the following general formula (G1).
[ chemical formula 1]
Figure BDA0002659073460000051
In the above general formula (G1), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, and R1Represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms. Furthermore, Y1And Y2Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms.
In another embodiment of the present invention, R in the general formula (G1)1Represents an aryl group having 6 to 25 carbon atoms, and the aryl group has two or more substituents each of which is any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a cycloalkyl group having 7 to 10 carbon atoms and having a crosslinked structure.
Another embodiment of the present invention is a compound represented by the following general formula (G2).
[ chemical formula 2]
Figure BDA0002659073460000061
In the above general formula (G2), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, and R1To R3Each independently represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms. Furthermore, Y 1And Y2Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms.
Another embodiment of the present invention is a compound represented by the following general formula (G3).
[ chemical formula 3]
Figure BDA0002659073460000071
In the above general formula (G3), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, Z1To Z3Each independently has a structure represented by any one of the general formula (Z-1), the general formula (Z-2) and the general formula (Z-3). In the general formula (Z-1), X1And X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms. Y is1To Y4Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms. In the general formula (Z-3), Ar1And Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms, and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3And Y4Any one of the same substituents as in (1).
Another embodiment of the present invention is a compound represented by the following general formula (G4).
[ chemical formula 4]
Figure BDA0002659073460000091
In the above general formula (G4), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, Z 1And Z2Each independently has a structure represented by any one of the general formula (Z-4), the general formula (Z-5) and the general formula (Z-6). In the general formula (Z-4), X1And X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms. Y is1To Y6Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms. In the general formula (Z-6), Ar1And Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms, and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3、Y4、Y5And Y6Any one of the same substituents as in (1).
Another embodiment of the present invention is a compound represented by the following general formula (G5).
[ chemical formula 5]
Figure BDA0002659073460000101
In the above general formula (G5), Z1To Z3Each independently has a structure represented by any one of the general formula (Z-1), the general formula (Z-2) and the general formula (Z-3). In the general formula (Z-1), X1And X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms. Y is1To Y4Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms. In the general formula (Z-3), Ar 1And Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms, and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3And Y4Any one of the same substituents as in (1). Furthermore, R4To R11Each independently represents any one of hydrogen, an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 25 carbon atoms.
Another embodiment of the present invention is a compound represented by the following general formula (G6).
[ chemical formula 6]
Figure BDA0002659073460000121
In the above general formula (G6), Z1And Z2Each independently has a structure represented by any one of the general formula (Z-4), the general formula (Z-5) and the general formula (Z-6). In the general formula (Z-4), X1And X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms. Y is1To Y6Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms. In the general formula (Z-6), Ar1And Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms, and Ar 1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3And Y4Any one of the same substituents as in (1). Furthermore, R4To R11Each independently represents any one of hydrogen, an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 25 carbon atoms.
Further, another embodiment of the present invention is a compound represented by structural formula (100).
[ chemical formula 7]
Figure BDA0002659073460000131
Another embodiment of the present invention is a light-emitting device using the compound according to one embodiment of the present invention. In addition, one embodiment of the present invention also includes a light-emitting device in which an EL layer or a light-emitting layer in the EL layer between a pair of electrodes contains the compound according to one embodiment of the present invention. In addition to the above light-emitting device, the present invention also includes a light-emitting device including a layer which is in contact with an electrode and includes an organic compound (e.g., a cap layer). Further, a light-emitting device including a transistor, a substrate, or the like is included in the scope of the invention in addition to the light-emitting device. In addition to the light emitting device, an electronic device and a lighting device including a microphone, a camera, an operation button, an external connection portion, a housing, a cover, a support base, a speaker, and the like are also included in the scope of the present invention.
One embodiment of the present invention includes not only a light-emitting device including a light-emitting device but also a lighting device including a light-emitting device. Therefore, the light-emitting device in this specification refers to an image display device or a light source (including a lighting device). In addition, the light-emitting device further includes the following modules: the light emitting device is mounted with a module of a connector such as FPC (flexible printed circuit) or TCP (tape carrier package); a module with a printed circuit board arranged at the end of the TCP; or a module in which an IC (integrated circuit) is directly mounted to a light emitting device by a COG (chip on glass) method.
According to one mode of the present invention, a novel compound can be provided. According to one embodiment of the present invention, a novel compound which can be used for a light-emitting device can be provided. Further, according to one embodiment of the present invention, a novel compound which can be used for an EL layer of a light-emitting device can be provided. Further, according to one embodiment of the present invention, a light-emitting device with high light-emitting efficiency can be provided. Further, according to one embodiment of the present invention, a light-emitting device with high reliability can be provided. Further, according to one embodiment of the present invention, a novel light-emitting device can be provided. Further, according to one embodiment of the present invention, a novel light-emitting device, a novel electronic device, or a novel lighting device can be provided.
Note that the description of the above effects does not hinder the existence of other effects. One embodiment of the present invention does not necessarily have all the effects described above. Effects other than the above-described effects can be understood and derived from the descriptions in the specification, drawings, claims, and the like.
Drawings
Fig. 1A is a diagram showing a structure of a light emitting device, and fig. 1B is a diagram illustrating a light emitting layer;
fig. 2A is a schematic diagram of energy transfer between a guest material and a host material in the related art, and fig. 2B is a schematic diagram of energy transfer between a compound (guest material) and a host material in one embodiment of the present invention;
fig. 3A is a schematic view of energy transfer between compounds in a light-emitting layer, fig. 3B is a schematic view of energy transfer between compounds in a light-emitting layer, and fig. 3C is a schematic view of energy transfer between compounds in a light-emitting layer;
fig. 4A is a schematic view of energy transfer between compounds in a light-emitting layer, fig. 4B is a schematic view of energy transfer between compounds in a light-emitting layer, and fig. 4C is a schematic view of energy transfer between compounds in a light-emitting layer;
fig. 5A is a schematic view of energy transfer between compounds in a light-emitting layer, and fig. 5B is a schematic view of energy transfer between compounds in a light-emitting layer;
Fig. 6A and 6B are diagrams illustrating a structure of a light emitting device;
fig. 7A, 7B, and 7C are diagrams illustrating a light-emitting device;
fig. 8A is a plan view illustrating a light emitting device, and fig. 8B is a sectional view illustrating the light emitting device;
fig. 9A is a diagram illustrating a mobile computer, fig. 9B is a diagram illustrating a portable image reproduction device, fig. 9C is a diagram illustrating a digital camera, fig. 9D is a diagram illustrating a portable information terminal, fig. 9E is a diagram illustrating a portable information terminal, fig. 9F is a diagram illustrating a television device, and fig. 9G is a diagram illustrating a portable information terminal;
fig. 10A, 10B, and 10C are diagrams illustrating foldable portable information terminals;
fig. 11A and 11B are diagrams illustrating an automobile;
fig. 12 is a diagram illustrating a lighting device;
fig. 13 is a diagram illustrating a lighting device;
FIG. 14 shows a schematic view of an organic compound represented by the structural formula (100)1H-NMR spectrum;
FIG. 15 is an ultraviolet-visible absorption spectrum and an emission spectrum of the organic compound represented by the structural formula (100);
fig. 16 is a diagram illustrating a light emitting device;
fig. 17 is a graph showing current density-luminance characteristics of the light emitting devices 1-1 to 1-5;
fig. 18 is a graph showing voltage-luminance characteristics of the light emitting devices 1-1 to 1-5;
Fig. 19 is a graph showing luminance-current efficiency characteristics of the light emitting devices 1-1 to 1-5;
fig. 20 is a graph showing voltage-current density characteristics of the light emitting devices 1-1 to 1-5;
fig. 21 is a graph showing electroluminescence spectra of the light emitting devices 1-1 to 1-5;
fig. 22 is a graph showing current density-luminance characteristics of the light emitting devices 2-1 to 2-5;
fig. 23 is a graph showing voltage-luminance characteristics of the light emitting devices 2-1 to 2-5;
fig. 24 is a graph showing luminance-current efficiency characteristics of the light emitting devices 2-1 to 2-5;
fig. 25 is a graph showing voltage-current density characteristics of the light emitting devices 2-1 to 2-5;
fig. 26 is a graph showing electroluminescence spectra of the light emitting devices 2-1 to 2-5;
FIG. 27 is a drawing showing a method for producing an organic compound represented by the structural formula (102)1H-NMR spectrum;
FIG. 28 is an ultraviolet-visible absorption spectrum and an emission spectrum of the organic compound represented by the structural formula (102);
FIG. 29 shows a schematic view of an organic compound represented by the structural formula (116)1H-NMR spectrum;
FIG. 30 is an ultraviolet-visible absorption spectrum and an emission spectrum of the organic compound represented by the structural formula (116);
FIG. 31 is a drawing showing an example of an organic compound represented by the structural formula (120) 1H-NMR spectrum;
FIG. 32 is an ultraviolet-visible absorption spectrum and an emission spectrum of the organic compound represented by the structural formula (120);
fig. 33 is a graph showing the reliability test results of the light emitting devices 1-1 to 1-5;
fig. 34 is a graph showing the reliability test results of the light emitting devices 2-1 to 2-5;
fig. 35 is a graph showing current density-luminance characteristics of the light emitting devices 3-1 to 3-5;
fig. 36 is a graph showing voltage-luminance characteristics of the light emitting devices 3-1 to 3-5;
fig. 37 is a graph showing luminance-current efficiency characteristics of the light emitting devices 3-1 to 3-5;
fig. 38 is a graph showing voltage-current density characteristics of the light emitting devices 3-1 to 3-5;
fig. 39 is a graph showing luminance-external quantum efficiency characteristics of the light emitting devices 3-1 to 3-5;
fig. 40 is a graph showing electroluminescence spectra of the light emitting devices 3-1 to 3-5;
fig. 41 is a graph showing current density-luminance characteristics of the light emitting devices 4-1 to 4-5;
fig. 42 is a graph showing voltage-luminance characteristics of the light emitting devices 4-1 to 4-5;
fig. 43 is a graph showing luminance-current efficiency characteristics of the light emitting devices 4-1 to 4-5;
fig. 44 is a graph showing voltage-current density characteristics of the light emitting devices 4-1 to 4-5;
Fig. 45 is a graph showing luminance-external quantum efficiency characteristics of the light emitting devices 4-1 to 4-5;
fig. 46 is a graph showing electroluminescence spectra of the light emitting devices 4-1 to 4-5;
fig. 47 is a graph showing the reliability test results of the light emitting devices 4-1 to 4-5;
fig. 48 is a graph showing current density-luminance characteristics of the light emitting devices 5-1 to 5;
fig. 49 is a graph showing voltage-luminance characteristics of the light emitting devices 5-1 to 5;
fig. 50 is a graph showing luminance-current efficiency characteristics of the light emitting devices 5-1 to 5;
fig. 51 is a graph showing voltage-current density characteristics of the light emitting devices 5-1 to 5;
fig. 52 is a graph showing luminance-external quantum efficiency characteristics of the light emitting devices 5-1 to 5;
fig. 53 is a graph showing electroluminescence spectra of the light emitting device 5-1 to the light emitting device 5-5;
fig. 54 is a graph showing current density-luminance characteristics of the light emitting devices 6-1 to 6-5;
fig. 55 is a graph showing voltage-luminance characteristics of the light emitting devices 6-1 to 6-5;
fig. 56 is a graph showing luminance-current efficiency characteristics of the light emitting devices 6-1 to 6-5;
fig. 57 is a graph showing voltage-current density characteristics of the light emitting devices 6-1 to 6-5;
Fig. 58 is a graph showing luminance-external quantum efficiency characteristics of the light emitting devices 6-1 to 6-5;
fig. 59 is a graph showing electroluminescence spectra of the light emitting devices 6-1 to 6-5;
fig. 60 is a graph showing the reliability test results of the light emitting devices 6-1 to 6-5;
fig. 61 is a graph showing current density-luminance characteristics of the light emitting devices 7-1 to 7-5;
fig. 62 is a graph showing voltage-luminance characteristics of the light emitting devices 7-1 to 7-5;
fig. 63 is a graph showing luminance-current efficiency characteristics of the light emitting devices 7-1 to 7-5;
fig. 64 is a graph showing voltage-current density characteristics of the light emitting devices 7-1 to 7-5;
fig. 65 is a graph showing luminance-external quantum efficiency characteristics of the light emitting devices 7-1 to 7-5;
fig. 66 is a graph showing electroluminescence spectra of the light emitting devices 7-1 to 7-5;
fig. 67 is a graph showing the reliability test results of the light emitting devices 7-1 to 7-5;
fig. 68 is a graph showing current density-luminance characteristics of the light emitting devices 8-1 to 8-5;
fig. 69 is a graph showing voltage-luminance characteristics of the light emitting devices 8-1 to 8-5;
fig. 70 is a graph showing luminance-current efficiency characteristics of the light emitting devices 8-1 to 8-5;
Fig. 71 is a graph showing voltage-current density characteristics of the light emitting devices 8-1 to 8-5;
fig. 72 is a graph showing luminance-external quantum efficiency characteristics of the light emitting devices 8-1 to 8-5;
fig. 73 is a graph showing electroluminescence spectra of the light emitting devices 8-1 to 8-5;
fig. 74 is a graph showing the reliability test results of the light emitting devices 8-1 to 8-5.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the following description, and the mode and the details thereof may be changed into various forms without departing from the spirit and the scope of the present invention. Therefore, the present invention should not be construed as being limited to the description of the embodiments shown below.
For ease of understanding, the positions, sizes, ranges, and the like of the respective components shown in the drawings and the like do not indicate actual positions, sizes, ranges, and the like. Accordingly, the disclosed invention is not necessarily limited to the positions, sizes, ranges, etc., disclosed in the drawings and the like.
Note that in this specification and the like, when the structure of the invention is described with reference to the drawings, symbols indicating the same parts may be used in common in different drawings.
Further, in this specification and the like, singlet excited state (S)*) Refers to a singlet state with excitation energy. Further, the S1 energy level is the lowest energy level of the singlet excited levels, which means the excited level of the lowest singlet excited state (S1 state). Further, triplet excited state (T)*) Refers to a triplet state having excitation energy. Further, the T1 energy level is the lowest energy level of the triplet excited energy levels, which means the excited energy level of the lowest triplet excited state (T1 state). In addition, in this specification and the like, though only "singlet excited state" and "singlet excited level" are mentionedBut sometimes represent the S1 state and the S1 level. In addition, although only the "triplet excited state" and the "triplet excited level" are described, the T1 state and the T1 level are sometimes indicated.
In the present specification and the like, the fluorescent substance refers to a compound that emits light in a visible light region or a near infrared region when returning from a singlet excited state to a ground state. The phosphorescent substance refers to a compound that emits light in a visible light region or a near infrared region at room temperature when returning from a triplet excited state to a ground state. In other words, the phosphorescent substance refers to one of compounds capable of converting triplet excitation energy into light emission.
Embodiment mode 1
In this embodiment, a compound according to one embodiment of the present invention will be described. A compound according to one embodiment of the present invention is a compound represented by the following general formula (G1).
[ chemical formula 8]
Figure BDA0002659073460000271
In the above general formula (G1), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, and R1Represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms. Furthermore, Y1And Y2Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms.
In another embodiment of the present invention, R in the general formula (G1)1Represents an aryl group having 6 to 25 carbon atoms, and the aryl group has two or more substituents each of which is any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a cycloalkyl group having 7 to 10 carbon atoms and having a crosslinked structure.
Another embodiment of the present invention is a compound represented by the following general formula (G2).
[ chemical formula 9]
Figure BDA0002659073460000291
In the above general formula (G2), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, and R 1To R3Each independently represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms. Furthermore, Y1And Y2Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms.
Another embodiment of the present invention is a compound represented by the following general formula (G3).
[ chemical formula 10]
Figure BDA0002659073460000301
In the above general formula (G3), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, Z1To Z3Each independently has a structure represented by any one of the general formula (Z-1), the general formula (Z-2) and the general formula (Z-3). In the general formula (Z-1), X1And X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms. Y is1To Y4Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms. In the general formula (Z-3), Ar1And Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms, and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3And Y4Any one of the same substituents as in (1).
Another embodiment of the present invention is a compound represented by the following general formula (G4).
[ chemical formula 11]
Figure BDA0002659073460000311
In the above general formula (G4), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, Z1And Z2Each independently has a structure represented by any one of the general formula (Z-4), the general formula (Z-5) and the general formula (Z-6). In the general formula (Z-4), X1And X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms. Y is1To Y6Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms. In the general formula (Z-6), Ar1And Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms, and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3、Y4、Y5And Y6Any one of the same substituents as in (1).
Another embodiment of the present invention is a compound represented by the following general formula (G5).
[ chemical formula 12]
Figure BDA0002659073460000331
In the above general formula (G5), Z1To Z3Each independently has a structure represented by any one of the general formula (Z-1), the general formula (Z-2) and the general formula (Z-3). In the general formula (Z-1), X1And X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms. Y is 1To Y4Each independently represents a cross-linked junctionCycloalkyl groups having 7 to 10 structural carbon atoms. In the general formula (Z-3), Ar1And Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms, and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3And Y4Any one of the same substituents as in (1). Furthermore, R4To R11Each independently represents any one of hydrogen, an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 25 carbon atoms.
Another embodiment of the present invention is a compound represented by the following general formula (G6).
[ chemical formula 13]
Figure BDA0002659073460000351
In the above general formula (G6), Z1And Z2Each independently has a structure represented by any one of the general formula (Z-4), the general formula (Z-5) and the general formula (Z-6). In the general formula (Z-4), X1And X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms. Y is1To Y6Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms. In the general formula (Z-6), Ar 1And Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms, and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3And Y4Any one of the same substituents as in (1). Furthermore, R4To R11Each independently represents hydrogen, an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a substituted or unsubstituted carbon atomIs any one of aryl groups of 6 to 25.
A compound according to one embodiment of the present invention is a material (a fluorescent substance) having a function of converting singlet excitation energy into light emission, and thus can be used as a guest material together with a host material in a light-emitting layer of a light-emitting device. A compound according to one embodiment of the present invention includes a light-emitting body that contributes to light emission and a protecting group that can suppress transfer of triplet excitation energy by the dexter mechanism from a host material to the compound. The luminophores contained in the compounds according to one embodiment of the present invention are fused aromatic rings or fused heteroaromatic rings, and the protecting groups contained in the compounds according to one embodiment of the present invention are groups contained in each of at least two diarylamino groups contained in the compounds according to one embodiment of the present invention, and the number of the groups is 2 or more. Specifically, the protective group included in the compound according to one embodiment of the present invention is any of a cycloalkyl group having 7 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms, which have a crosslinked structure.
In addition, in the compound according to one embodiment of the present invention, two or more diarylamino groups including a protecting group are bonded to a light-emitting body at symmetrical positions, whereby quantum yield can be improved. In addition, in the compound according to one embodiment of the present invention, a diarylamino group is used, whereby sublimation property can be maintained while suppressing increase in molecular weight.
In addition, in the compound according to one embodiment of the present invention, the protecting group is bonded to an aryl group in a diarylamino group which is bonded to the light-emitting body, and thus the protecting group can be disposed so as to cover the light-emitting body so that the host material is distant from the light-emitting body to maintain a distance between the two which is less likely to cause energy transfer by the dexter mechanism.
In the general formula (G1), the general formula (G2), the general formula (G3) and the general formula (G4), examples of the condensed aromatic ring having 10 to 30 carbon atoms or the condensed heteroaromatic ring having 10 to 30 carbon atoms include a phenanthrene skeleton, a stilbene skeleton, an acridone skeleton, a phenoxazine skeleton, a phenothiazine skeleton and the like. Can also liftA naphthalene skeleton, an anthracene skeleton, a fluorene skeleton, a naphthalene skeleton, a anthracene skeleton, a fluorene skeleton, a fluorine-containing compound and a fluorine-containing compound, wherein the naphthalene skeleton, the anthracene skeleton, the fluorene skeleton and the fluorine-containing compound can further improve,
Figure BDA0002659073460000381
A skeleton, a triphenylene skeleton, a tetracene skeleton, a pyrene skeleton, a perylene skeleton, a coumarin skeleton, a quinacridone skeleton, a naphtho-dibenzofuran skeleton, or the like.
In the general formula (G3), the general formula (G4), the general formula (G5) and the general formula (G6), examples of the aromatic hydrocarbon having 6 to 13 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group and the like.
Specific examples of the alkyl group having 3 to 10 carbon atoms in the general formula (G1), the general formula (G3), the general formula (G4), the general formula (G5) and the general formula (G6) include a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a decyl group, and the like.
Specific examples of the cycloalkyl group having 3 to 10 carbon atoms in the general formula (G1), the general formula (G3), the general formula (G4), the general formula (G5) and the general formula (G6) include cyclopropyl, cyclobutyl, cyclohexyl and the like. When the cycloalkyl group has a substituent, examples of the substituent include an alkyl group having 1 to 7 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group, a cycloalkyl group having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and an 8, 9, 10-trinorborneyl group, and an aryl group having 6 to 12 carbon atoms such as a phenyl group, a naphthyl group and a biphenyl group.
Specific examples of the cycloalkyl group having 7 to 10 carbon atoms and having a crosslinking structure in the general formula (G1), the general formula (G2), the general formula (G3), the general formula (G4), the general formula (G5) and the general formula (G6) include adamantyl and bicyclo [2.2.1 ]Heptyl, tricyclo [5.2.1.02，6]Decyl, noradamantyl, bornyl, and the like.
Specific examples of the trialkylsilyl group having 3 to 12 carbon atoms in the general formula (G1), the general formula (G3), the general formula (G4), the general formula (G5), and the general formula (G6) include trimethylsilyl group, triethylsilyl group, and tert-butyldimethylsilyl group.
In the general formula (G1), the general formula (G2), the general formula (G3), the general formula (G4), the general formula (G5) and the general formula (G6), when any of the fused aromatic ring, the fused heteroaromatic ring, the aromatic hydrocarbon group having 6 to 13 carbon atoms or the cycloalkyl group having 3 to 10 carbon atoms has a substituent, examples of the substituent include an alkyl group having 1 to 7 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group and a hexyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tert-butyl group, a pentyl group and a hexyl group, a cycloalkyl group having 5 to 7 carbon atoms such as a trinitrophenyl group, a naphthyl group and a biphenyl group, and the like.
In the general formula (G1), the general formula (G2), the general formula (G5) and the general formula (G6), specific examples of the aryl group having 6 to 25 carbon atoms include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a spirofluorenyl group and the like. When the aryl group has a substituent, examples of the substituent include the alkyl group having 3 to 10 carbon atoms, the substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and the trialkylsilyl group having 3 to 12 carbon atoms.
Specific examples of the compounds represented by the above general formulae (G1) to (G6) are shown by the following structural formulae (100) to (136). Note that specific examples of the compounds represented by the general formulae (G1) to (G6) are not limited thereto.
[ chemical formula 14]
Figure BDA0002659073460000421
[ chemical formula 15]
Figure BDA0002659073460000431
[ chemical formula 16]
Figure BDA0002659073460000441
[ chemical formula 17]
Figure BDA0002659073460000451
[ chemical formula 18]
Figure BDA0002659073460000461
[ chemical formula 19]
Figure BDA0002659073460000471
[ chemical formula 20]
Figure BDA0002659073460000481
< method for synthesizing organic Compound represented by the general formula (G1) >
The following describes a method for synthesizing a compound represented by general formula (G1).
[ chemical formula 21]
Figure BDA0002659073460000491
In the above general formula (G1), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, and R1Represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms. Furthermore, Y1And Y2Each independently represents any one of cycloalkyl groups having 7 to 10 carbon atoms and having a crosslinked structure.
The compound represented by the above general formula (G1) can be synthesized, for example, by the methods shown in the following synthesis scheme (S-1) and synthesis scheme (S-2).
First, compound 1 is coupled with compound 2 (arylamine) to obtain compound 3 (diamine compound) (synthesis scheme (S-1)).
[ chemical formula 22]
Figure BDA0002659073460000501
Then, compound 3 (diamine compound) and compound 4 (halogenated aryl) are coupled to obtain a compound represented by general formula (G1) (synthesis scheme (S-2)).
[ chemical formula 23]
Figure BDA0002659073460000511
Further, the compound represented by the above general formula (G1) can also be synthesized by the methods shown in the following synthesis scheme (S-3), synthesis scheme (S-4) and synthesis scheme (S-5).
First, compound 2 (arylamine) and compound 4 (halogenated aryl) are coupled to obtain compound 5 (amine compound) (synthesis scheme (S-3)).
[ chemical formula 24]
Figure BDA0002659073460000512
Further, compound 5 (amine compound) is coupled to give a compound represented by general formula (G1) (synthetic scheme (S-4)).
[ chemical formula 25]
Figure BDA0002659073460000521
Further, in the above-mentioned synthesis schemes (S-1) to (S-4), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, and R is1Represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms. Y is1And Y2Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atomsAny one of (1). Examples of the fused aromatic ring or fused heteroaromatic ring include
Figure BDA0002659073460000522
Phenanthrene, stilbene, acridone, phenoxazine, phenothiazine, pyrene, coumarin, quinacridone, perylene, tetracene, naphtho-bis-benzofuran, and the like, and anthracene is particularly preferably used.
Note that, in the case where the Buhward-Hartvich reaction using a palladium catalyst is carried out in the above-described synthesis schemes (S-1) to (S-4), X 10To X11Represents a halogen group or a trifluoromethanesulfonate group, and as a halogen, iodine, bromine or chlorine is preferred. In the above reaction, ligands such as palladium compounds such as bis (dibenzylideneacetone) palladium (0) and palladium (II) acetate, tris (tert-butyl) phosphine, tris (n-hexyl) phosphine, tricyclohexylphosphine, bis (1-adamantyl) -n-butylphosphine, and 2-dicyclohexylphosphino-2 ', 6 ' -dimethoxy-1, 1 ' -biphenyl can be used. In the above reaction, an organic base such as sodium tert-butoxide, an inorganic base such as potassium carbonate, cesium carbonate or sodium carbonate, or the like can be used. As the solvent, toluene, xylene, mesitylene, benzene, tetrahydrofuran, dioxane, or the like can be used. Note that the reagents that can be used in the above reaction are not limited to the above reagents.
The reactions carried out in the above-mentioned synthesis schemes (S-1) to (S-4) are not limited to the Buhward-Hartvisch reaction, and a Dow-Picea-Stille coupling reaction using an organotin compound, a coupling reaction using a Grignard reagent, an Ullmann reaction using copper or a copper compound, and the like can be used.
< method for synthesizing organic Compound represented by the general formula (G2) >
The following describes a method for synthesizing a compound represented by general formula (G2).
[ chemical formula 26]
Figure BDA0002659073460000541
In the general formula (G2), A represents a substituted or unsubstituted carbon atom number10 to 30 fused aromatic ring or substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, R1To R3Aryl groups having 6 to 25 carbon atoms each independently substituted or unsubstituted. Furthermore, Y1And Y2Each independently represents any one of cycloalkyl groups having 7 to 10 carbon atoms and having a crosslinked structure.
The compound represented by the above general formula (G2) can be synthesized, for example, by the method shown in the following synthesis scheme (S-5).
By coupling compound 5 (amine compound) and compound 7 (amine compound), a compound represented by general formula (G2) can be obtained (synthesis scheme (S-5)).
[ chemical formula 27]
Figure BDA0002659073460000551
Further, in the above synthesis scheme (S-5), A represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms, and R is1To R3Aryl groups having 6 to 25 carbon atoms each independently substituted or unsubstituted. Y is1And Y2Each independently represents any one of cycloalkyl groups having 7 to 10 carbon atoms and having a crosslinked structure. Examples of the fused aromatic ring or fused heteroaromatic ring include
Figure BDA0002659073460000561
Phenanthrene, stilbene, acridone, phenoxazine, phenothiazine, pyrene, coumarin, quinacridone, perylene, tetracene, naphtho-bis-benzofuran, and the like, and anthracene is particularly preferably used.
Note that, in the case where the Buhward-Hartvisch reaction using a palladium catalyst is carried out in the above synthesis scheme (S-5), X12To X13Represents a halogen group or a trifluoromethanesulfonate group, and as a halogen, iodine, bromine or chlorine is preferred. In the above reaction, a palladium compound such as bis (dibenzylideneacetone) palladium (0) or palladium (II) acetate, tri (tert-butyl) phosphine, tri (n-hexyl) phosphine, or the like can be used) Phosphine, tricyclohexylphosphine, bis (1-adamantyl) -n-butylphosphine, and 2-dicyclohexylphosphino-2 ', 6 ' -dimethoxy-1, 1 ' -biphenyl. In the above reaction, an organic base such as sodium tert-butoxide, an inorganic base such as potassium carbonate, cesium carbonate or sodium carbonate, or the like can be used. As the solvent, toluene, xylene, mesitylene, benzene, tetrahydrofuran, dioxane, or the like can be used. Note that the reagents that can be used in the above reaction are not limited to the above reagents.
The reaction carried out in the above synthesis scheme (S-5) is not limited to the Buhward-Hardwich reaction, and a Douglas-Picea-Stille coupling reaction using an organotin compound, a coupling reaction using a Grignard reagent, an Ullmann reaction using copper or a copper compound, or the like may be used.
In the above synthesis scheme (S-5), it is preferable that compound 6 is reacted with compound 5 to form a coupled body, and then the resultant coupled body is reacted with compound 7.
Although the method for synthesizing the compound according to one embodiment of the present invention has been described above, the present invention is not limited thereto, and may be synthesized by other synthesis methods.
Embodiment mode 2
In this embodiment mode, an example of a light-emitting device in which a compound according to one embodiment of the present invention is preferably used will be described. As shown in fig. 1A, the light-emitting device has a structure in which an EL layer 103 is interposed between a pair of electrodes including a first electrode 101 (corresponding to an anode in fig. 1A) and a second electrode 102 (corresponding to a cathode in fig. 1A), and the EL layer 103 includes at least a light-emitting layer 113 and may further include functional layers such as a hole injection layer 111, a hole transport layer 112, an electron transport layer 114, and an electron injection layer 115.
The light-emitting layer 113 includes a light-emitting substance (guest material) and a host material. In the light-emitting device, by applying a voltage between a pair of electrodes, electrons and holes are injected from the cathode and the anode, respectively, to the EL layer 103, and a current flows. At this time, in the light-emitting layer 113, carriers (electrons and holes) are recombined to form excitons, and excitation energy of the excitons is converted into light emission, whereby light emission can be obtained from the light-emitting device. In this embodiment mode, as shown in fig. 1B, the light-emitting layer 113 includes a compound 132 serving as an energy acceptor which functions as a light-emitting substance (guest material) and a compound 131 serving as an energy donor which functions as a host material. Therefore, in this embodiment, a case where a compound according to one embodiment of the present invention is used as a light-emitting substance (guest material) will be described. Further, the light-emitting layer 113 may contain a plurality of compounds serving as host materials.
Among excitons generated by recombination of carriers, a ratio of generating singlet excitons is 25% and a ratio of generating triplet excitons is 75%. Therefore, in order to improve the light emission efficiency of the light-emitting device, it is preferable that triplet excitons contribute to light emission in addition to singlet excitons. Here, the concept of energy transfer occurring between the guest material and the host material is explained with reference to fig. 2A and 2B. Fig. 2A shows a structure of a general guest material (fluorescent substance), and shows a concept of energy transfer between the guest material and a host material in the case of using the material. Fig. 2B shows the structure of the compound 132 according to one embodiment of the present invention, and shows the concept of energy transfer between a guest material and a host material in the case where the compound 132 is used as the guest material.
Fig. 2A shows the presence of a compound 131 serving as a host material and a fluorescent substance 124 serving as a guest material. The fluorescent substance 124 is a general fluorescent substance, and includes the light emitter 124a without including a protecting group.
Fig. 2B shows how a compound 131 serving as a host material and a compound (fluorescent substance) 132 serving as a guest material according to one embodiment of the present invention are present. The compound 132 is a fluorescent substance used as an energy acceptor in a light-emitting device, and includes a light-emitting substance 132a and a protecting group 132 b. Further, the protecting group 132b has a function of separating the compound (host material) 131 from the light emitter 132a by a distance that does not easily cause energy transfer based on the dexter mechanism from it to the light emitter 132 a.
As shown in fig. 2A and 2B, in the light-emitting layer 113, a compound 131 serving as a host material, and a fluorescent substance 124 and a compound (fluorescence) serving as a guest materialOptical substances) 132 are present in close proximity to each other. Therefore, as shown in fig. 2A, in the case where the fluorescent substance 124 has no protecting group, since the distance between the emitter 124a and the compound 131 is short, energy transfer based on the forster mechanism may occur as energy transfer from the compound 131 to the fluorescent substance 124 (path a in fig. 2A)6) And energy transfer based on the Dexter mechanism (Path A in FIG. 2A)7) Both sides of (1). When triplet excitation energy transfer based on the dexter mechanism from the host material to the guest material occurs to generate a triplet excited state of the guest material, in the case where the guest material is a fluorescent light-emitting substance, non-radiative deactivation of the triplet excitation energy occurs, which becomes one of causes of a decrease in light emission efficiency of the light-emitting device.
On the other hand, in fig. 2B, a compound (fluorescent substance) 132 serving as a guest material has a protecting group 132B, whereby the distance between a light emitter 132a and a compound 131 serving as a host material can be increased. This can suppress energy transfer by the Dexter mechanism (route A) 7)。
Here, a light-emitting body 124a included in the fluorescent substance 124 shown in fig. 2A and a light-emitting body 132A included in the compound (fluorescent substance) 132 shown in fig. 2B will be described. The light-emitting bodies (124a, 132a) are atomic groups (skeletons) that cause light emission in the fluorescent substance. The emitters (124a, 132a) generally have pi bonds, preferably comprise aromatic rings, more preferably have fused aromatic or fused heteroaromatic rings. Examples of the condensed aromatic ring or condensed heteroaromatic ring contained in the light-emitting bodies (124a, 132a) include a phenanthrene skeleton, a stilbene skeleton, an acridone skeleton, a phenoxazine skeleton, and a phenothiazine skeleton. Further, a naphthalene skeleton, an anthracene skeleton, a fluorene skeleton, a perylene skeleton, a polyamide skeleton, and a polyamide skeleton,
Figure BDA0002659073460000601
A skeleton, a triphenylene skeleton, a tetracene skeleton, a pyrene skeleton, a perylene skeleton, a coumarin skeleton, a quinacridone skeleton, a naphtho-dibenzofuran skeleton, or the like. In particular, an anthracene skeleton is particularly preferably used for the light-emitting body 132a included in the compound 132 according to one embodiment of the present invention.
Further, the T1 level of the protecting group 132B contained in the compound (fluorescent substance) 132 shown in fig. 2B is preferably higher than the T1 level of the light-emitting substance 132a and the compound 131 serving as a host material. Specific examples of the protecting group 132b contained in the compound 132 according to one embodiment of the present invention include a cycloalkyl group having 7 to 10 carbon atoms and having a crosslinked structure. Further, an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and the like can be mentioned. The inclusion of such a protecting group 132b allows formation of a bulky structure, and thus the distance between the emitter 132a of the compound 132 serving as a guest material and the compound 131 serving as a host material can be increased.
The structure of the light-emitting layer of the light-emitting device according to one embodiment of the present invention will be described below.
< structural example 1 of light-emitting layer >
This structural example shows the following case: a light-emitting layer 113 in the light-emitting device has a compound 131 serving as a host material and a compound 132 serving as a light-emitting substance (guest material), in which the compound 131 uses a TADF material, and the compound 132 serving as a light-emitting substance (guest material) uses a fluorescent light-emitting substance. Therefore, a compound according to one embodiment of the present invention is preferably used as the compound 132 which is a fluorescent substance. Fig. 3A shows an example of energy level correlation in the light-emitting layer 113 of the present structural example. The labels and symbols in fig. 3A are listed below.
Host (131): compound 131
Guest (132): compound 132
·TC1: t1 energy level of Compound 131
·SC1: s1 energy level of Compound 131
·SG: s1 energy level of Compound 132
·TG: t1 level of Compound 132
In the present structural example, compound 131 is a material in the form of TADF. Therefore, the compound 131 has a function of converting triplet excitation energy into singlet excitation energy by up-conversion (pathway a in fig. 3A)1). Compound 131 havingSinglet excitation energy is rapidly transferred to compound 132 (pathway A in FIG. 3A)2). At this time, S of Compound 131 C1And S of Compound 132GPreferably satisfies the relationship ofC1≥SG. Note that SC1This is the energy of the wavelength of the extrapolation line when the tail of the fluorescence spectrum of compound 131 on the short wavelength side is cut. SGRefers to the energy at the wavelength of the absorption end of the absorption spectrum of compound 132.
In this manner, the triplet excitation energy generated in the compound 131 passes through the pathway a1And route A2The transfer to the S1 level of the compound 132 as a guest material can cause the compound 132 to emit light with high efficiency, whereby the light emitting efficiency of the light emitting device can be improved. On the path A2In (b), compound 131 is used as an energy donor and compound 132 is used as an energy acceptor. However, in the light-emitting layer 113 of the light-emitting device shown in this structural example, in addition to the above, there is a path (path a in fig. 3A) through which triplet excitation energy generated in the compound 131 is transferred to the T1 energy level of the compound 1323) There is a competition between the two. Where this energy transfer takes place (path A)3) In the case of (3), triplet excitation energy in the compound 132 which is a fluorescent light-emitting substance does not contribute to light emission, and thus the light-emitting efficiency of the light-emitting device is lowered.
Generally, as an intermolecular energy transfer mechanism, a forster mechanism (dipole-dipole interaction) and a dexter mechanism (electron exchange interaction) are known. When the distance between the compound as an energy donor and the compound as an energy acceptor is 1nm or less, the dexter mechanism is dominant. Thus, when the concentration of the compound as an energy receptor is increased, the dexter mechanism is easily exhibited. Therefore, as in the present structural example, when the compound 132 as the energy acceptor is a fluorescent material having a low triplet excitation level, the triplet excitation energy of the compound 131 as the energy donor mainly passes through the path a based on the dexter mechanism when the concentration of the compound 132 is increased 3Transferred and then rendered radiation-free inactive. Therefore, to suppress the transit path A3Importantly, compound 131 and compound132 to maintain a distance that does not readily cause energy transfer based on the dexter mechanism.
Furthermore, the energy level T1 (T) of compound 132 as an energy receptorG) Most of the energy level is derived from the emitter contained in compound 132. Therefore, the distance between the emitters contained in the compound 131 and the compound 132 is increased to suppress the pathway a in the light-emitting layer 1133Is important.
As a method for increasing the distance between an energy donor and a luminophore contained in an energy acceptor, a method for reducing the concentration of the energy acceptor in a mixed film of these compounds is known. However, when the concentration of the energy acceptor is decreased, energy transfer based on the forster mechanism is also inhibited in addition to energy transfer based on the dexter mechanism from the energy donor to the energy acceptor. At this time, because the path A2Due to the foster mechanism, problems such as a decrease in light emission efficiency and a decrease in reliability of the light emitting device occur. On the other hand, a part of the structure of the compound according to one embodiment of the present invention includes a light-emitting body and a protecting group, and when the compound functions as an energy acceptor in the light-emitting layer 113, the protecting group has a function of increasing the distance between an energy donor and the light-emitting body. Therefore, in the case where a compound according to one embodiment of the present invention is used as the compound 132, the distance between the compound 132 and the compound 131 can be increased. In addition, the Dexter mechanism is dominant when the distance between the energy donor and the energy acceptor is 1nm or less, and the Forster mechanism is dominant when the distance between the energy donor and the energy acceptor is 1nm or more and 10nm or less. Therefore, the protecting group is preferably a bulky substituent which extends in a range of 1nm or more and 10nm or less from the luminophore, and the above-mentioned protecting group is preferably used as a protecting group contained in the compound of one embodiment of the present invention. Thus, when a compound according to one embodiment of the present invention is used as the compound 132, the energy transfer rate according to the forster mechanism can be increased while the energy transfer according to the dexter mechanism is suppressed even when the concentration of the compound 132 is increased. That is, on the one hand, from the S1 energy level (S) of compound 131 C1) To the S1 energy level (S) of compound 132G) Transfer of singlet excitation energy (Path A)2) Easily occurs, on the other hand, the T1 energy level (T) from compound 131 to compound 132G) Transfer of triplet excitation energy (pathway A)3: energy transfer based on the dexter mechanism) is suppressed, whereby the accompanying path a can be suppressed3The light emitting efficiency of the light emitting device is improved while the light emitting efficiency of the energy transfer is reduced. In addition, by increasing the energy transfer rate based on the forster mechanism, the excitation lifetime of the energy acceptor in the light emitting layer becomes short, and thus the reliability of the light emitting device can be improved. Specifically, the concentration of the compound 132 in the light-emitting layer 113 is preferably 2 wt% or more and 50 wt% or less, more preferably 5 wt% or more and 30 wt% or less, and further preferably 5 wt% or more and 20 wt% or less, with respect to the compound 131 as an energy donor.
< structural example 2 of light-emitting layer >
This structural example shows the following case: the light-emitting layer 113 in the light-emitting device includes a compound 131, a compound 132, and a compound 133, and the compound 131 and the compound 133 form a combination of exciplexes, and a fluorescent light-emitting substance is used as the compound 132 which is used as a light-emitting substance (guest material) (in the case of using ExEF). Therefore, a compound according to one embodiment of the present invention is preferably used as the compound 132 which is a fluorescent substance. Fig. 3B shows an example of energy level correlation in the light-emitting layer 113 of the present structural example. The labels and symbols in FIG. 3B are listed below.
Comp (131): compound 131
Comp (133): compound 133
Guest (132): compound 132
·SC1: s1 energy level of Compound 131
·TC1: t1 energy level of Compound 131
·SC3: s1 level of Compound 133
·TC3: t1 level of Compound 133
·SG: s1 energy level of Compound 132
·TG: t1 level of Compound 132
·SF: exciplexS1 energy level of
·TF: t1 energy level of exciplex
The combination of the compound 131 and the compound 133 may be any combination as long as it can form an exciplex, and one of them is preferably a compound having a function of transporting holes (hole-transporting property) and the other is preferably a compound having a function of transporting electrons (electron-transporting property). In this case, a donor-acceptor type exciplex is easily formed, and an exciplex can be efficiently formed. Further, when the combination of the compound 131 and the compound 133 is a combination of a compound having a hole-transporting property and a compound having an electron-transporting property, the balance of carriers can be easily controlled by adjusting the mixing ratio thereof. Specifically, the compound having a hole-transporting property: the compound having an electron-transporting property is preferably in the range of 1: 9 to 9: 1 (weight ratio). Further, by having this structure, the balance of carriers can be easily controlled, and thus the carrier recombination region can also be easily controlled.
Further, as a combination of host materials which efficiently form an exciplex, it is preferable that one of the compound 131 and the compound 133 has a higher HOMO level than the other, and that one has a higher LUMO level than the other. The HOMO level of compound 131 may be equal to the HOMO level of compound 133, or the LUMO level of compound 131 may be equal to the LUMO level of compound 133.
Note that the LUMO level and HOMO level of a compound can be determined from the electrochemical characteristics (reduction potential and oxidation potential) of the compound measured by Cyclic Voltammetry (CV) measurement.
As shown in FIG. 3B, the exciplex composed of compound 131 and compound 133 has S1 level (S)E) And T1 energy level (T)E) Become adjacent energy levels (see path A in FIG. 3B)6)。
Excitation level (S) of exciplexEAnd TE) The energy level (S) of S1 is higher than that of each of the exciplex-forming substances (Compound 131 and Compound 133)C1And SC3) Low, so that lower excitation energy can be usedAn excited state is formed. Thereby, the driving voltage of the light emitting device can be reduced.
Because of the S1 energy level (S) of the exciplexE) And a T1 energy level (T)E) Are adjacent energy levels, and therefore, are likely to cause intersystem crossing, and have TADF characteristics. Therefore, the exciplex has a function of converting triplet excitation energy into singlet excitation energy by up-conversion (pathway A of FIG. 3B) 7). The singlet excitation energy of the exciplex can be rapidly transferred to the compound 132 (FIG. 3B, route A)8). In this case, it is preferable to satisfy SE≥SG. On the path A8The exciplex is used as an energy donor and the compound 132 is used as an energy acceptor. Specifically, it is preferable that a line is drawn at the tail of the exciplex on the short-wavelength side of the fluorescence spectrum, and the energy of the extrapolated wavelength is set to SEThe energy of the wavelength at the absorption edge of the absorption spectrum of the compound 132 is set to SGAt this time, S is satisfiedE≥SG。
In order to increase the TADF characteristics, it is preferable that the T1 energy levels of the compound 131 and the compound 133, i.e., TC1And TC3Is TEThe above. As an index thereof, it is preferable that the emission peak wavelength on the shortest wavelength side of the phosphorescence spectra of both the compound 131 and the compound 133 is equal to or less than the maximum emission peak wavelength of the exciplex. Alternatively, it is preferable that a line is cut at the tail of the exciplex on the short-wavelength side of the fluorescence spectrum, and the energy of the extrapolated wavelength is set to SEThe tails of the phosphorescent spectra of the compounds 131 and 133 at the short wavelengths are each cut off to form a tangent, and the energy at the wavelength of this extrapolated line is set as T of each compoundC1And TC3In this case, S is preferable E-TC1Less than or equal to 0.2eV and SE-TC3≤0.2eV。
By passing triplet excitation energy generated in the light-emitting layer 113 through the path a6And route A8The transfer to the S1 level of the compound 132 as a guest material can cause the compound 132 to emit light. Therefore, by using a material forming a combination of exciplexes for the light-emitting layer 113, the light-emitting efficiency of the fluorescent light-emitting device can be improved. However, there is also a path (path a in fig. 3B) through which triplet excitation energy generated in the light-emitting layer 113 is transferred to the T1 level of the compound 1329) There is a competition between the two. Where this energy transfer takes place (path A)9) In the case of (3), triplet excitation energy in the compound 132 which is a fluorescent light-emitting substance does not contribute to light emission, and thus the light-emitting efficiency of the light-emitting device is lowered.
To suppress this energy transfer (path A in FIG. 3B)9) As described in the above structural example 1, it is important that the distance between the exciplex formed from the compound 131 and the compound 133 and the compound 132 and the distance between the exciplex and the light-emitting substance contained in the compound 132 are long.
A part of the structure of the compound according to one embodiment of the present invention includes a light-emitting body and a protecting group, and when the compound is used as an energy acceptor in the light-emitting layer 113, the protecting group has a function of increasing the distance between an energy donor and the light-emitting body. Thus, when a compound according to one embodiment of the present invention is used as the compound 132, the distance between the exciplex formed from the compound 131 and the compound 133 and the compound 132 can be increased even when the concentration of the compound 132 is increased, and the energy transfer rate by the ford mechanism can be increased while suppressing the energy transfer by the dexter mechanism. Therefore, when a compound according to one embodiment of the present invention is used as the compound 132, the energy level of S1 (S) from the exciplex to the compound 132 is one aspect G) Transfer of triplet excitation energy (path a in fig. 3B)6And route A8) Readily occuring, on the other hand, T1 energy level (T) from exciplex to compound 132G) Transfer of triplet excitation energy (pathway A)9: energy transfer based on the dexter mechanism) is suppressed, whereby the accompanying path a can be suppressed9The light emitting efficiency of the light emitting device is improved while the light emitting efficiency of the energy transfer is reduced. In addition, the reliability of the light emitting device can be improved.
In this specification, the path a may be defined as6To A8The process of (2) is called ExSET (Exciplex-Singlet Energy Transfer: Exciplex-Singlet Energy Transfer) or ExEF (Exciplex-enhance)ed Fluorescence: exciplex enhanced fluorescence). In other words, in the light-emitting layer 113 in the present specification, supply of excitation energy from the exciplex to the fluorescent material is generated.
< structural example 3 of light-emitting layer >
This structural example shows the following case: the light-emitting layer 113 in the light-emitting device includes a compound 131, a compound 132, and a compound 133, and the compound 131 and the compound 133 form a combination of exciplexes, and a fluorescent light-emitting substance is used as the compound 132 which is used as a light-emitting substance (guest material) (in the case of using ExEF). The difference from the above structural example 2 is that the compound 133 is a phosphorescent material. Further, a compound according to one embodiment of the present invention is preferably used as the compound 132 which is a fluorescent substance. Fig. 3C shows an example of energy level correlation in the light-emitting layer 113 of the present structural example. The explanation of the reference numerals and symbols in fig. 3C is omitted because they are the same as those in fig. 3B.
In the present structural example, a compound containing a heavy atom is used for one of the compounds forming the exciplex. Thus, intersystem crossing between the singlet excited state and the triplet excited state is promoted. Therefore, an exciplex capable of transitioning from a triplet excited state to a singlet ground state (i.e., capable of exhibiting phosphorescence) can be formed. In this case, unlike a general exciplex, the triplet excitation level (T) of the exciplex is differentE) Is the energy level of an energy donor, thus TEPreferably, the singlet excitation level (S) of the compound 132 as a light-emitting materialG) The above. Specifically, it is preferable that a tangent is drawn at the tail on the short-wavelength side of the emission spectrum of the exciplex using heavy atoms, and the energy of the wavelength of this extrapolated line is set to TEThe energy of the wavelength at the absorption edge of the absorption spectrum of the compound 132 is set to SGAt this time, T is satisfiedE≥SG。
When the energy levels are correlated with each other, the triplet excitation energy of the generated exciplex can be adjusted from the triplet excitation level (T) of the exciplexF) Singlet excitation level (S) to compound 132G) Energy transfer is performed. Note the S1 energy level (S) of the exciplexE) And TEnergy level 1 (T)E) Adjacent to each other, and thus it is sometimes difficult to clearly distinguish fluorescence and phosphorescence in an emission spectrum. In this case, fluorescence and phosphorescence may be distinguished according to the emission lifetime.
The phosphorescent material used in the above structure preferably contains heavy atoms such as Ir, Pt, Os, Ru, Pd, and the like. On the other hand, in the present structural example, the phosphorescent material is also used as an energy donor, and thus the quantum yield thereof can be both high and low. That is, the energy transfer from the triplet excitation level of the exciplex to the singlet excitation level of the guest material may be allowed. In the energy transfer from the exciplex composed of the phosphorescent material or the phosphorescent material to the guest material, the energy transfer from the triplet excitation level of the energy donor to the singlet excitation level of the guest material (energy acceptor) is preferable because the energy transfer is allowed.
Therefore, as shown in fig. 3C, in the light-emitting layer 113 of the light-emitting device shown in this structural example, triplet excitation energy of the exciplex passes through the path a8Without going through path a in fig. 3C7Process) to the S1 energy level (S) of the guest materialG). That is, the path a6 and the path a can be passed8The process of (3) transfers the triplet excitation energy and the singlet excitation energy to the S1 energy level of the guest material. On the path A8The exciplex is used as an energy donor and the compound 132 is used as an energy acceptor. However, in the light-emitting layer 113 of the light-emitting device shown in this structural example, in addition to the above, there is a path (path a in fig. 3C) through which the triplet excitation energy of the exciplex is transferred to the T1 level of the compound 132 9) There is a competition between the two. Where this energy transfer takes place (path A)9) In the case of (3), triplet excitation energy in the compound 132 which is a fluorescent light-emitting substance does not contribute to light emission, and thus the light-emitting efficiency of the light-emitting device is lowered.
To suppress this energy transfer (path A)9) As described in the above structural example 1, it is important that the distance between the compound 131 and the compound 132 and the distance between the compound 131 and the light-emitting substance contained in the compound 132 are long.
One mode of the inventionThe compound (2) has a structure including a light-emitting body and a protecting group, and when the compound is used as an energy acceptor in the light-emitting layer 113, the protecting group has a function of increasing the distance between an energy donor and the light-emitting body. Thus, when a compound according to one embodiment of the present invention is used as the compound 132, the distance between the exciplex formed from the compound 131 and the compound 133 and the compound 132 can be increased even when the concentration of the compound 132 is increased, and the energy transfer rate by the ford mechanism can be increased while suppressing the energy transfer by the dexter mechanism. Therefore, when a compound according to one embodiment of the present invention is used as the compound 132, the energy level of S1 (S) from the exciplex to the compound 132 is one aspect G) Transfer of triplet excitation energy (pathway A)6And route A8) Readily occuring, on the other hand, T1 energy level (T) from exciplex to compound 132G) Transfer of triplet excitation energy (pathway A)9: energy transfer based on the dexter mechanism) is suppressed, whereby the accompanying path a can be suppressed9The light emitting efficiency of the light emitting device is improved while the light emitting efficiency of the energy transfer is reduced.
< structural example 4 of light-emitting layer >
This structural example shows the following case: the light-emitting layer 113 in the light-emitting device includes three kinds of substances, that is, a compound 131, a compound 132, and a compound 133, and the compound 131 and the compound 133 are a combination forming an exciplex, and a fluorescent light-emitting substance is used as the compound 132 which serves as a light-emitting substance (guest material) (in the case of using FxFF). Therefore, a compound according to one embodiment of the present invention is preferably used as the compound 132 which is a fluorescent substance. Further, the difference from the above structural example 3 is that the compound 133 is a material having TADF properties. Further, fig. 4A shows an example of energy level correlation in the light-emitting layer 113 of the present structural example. The explanation of the reference numerals and symbols in fig. 4A is omitted because they are the same as those in fig. 3B.
In the present structural example, the compound 133 is a TADF material. Therefore, the compound 133 in which no exciplex is formed has a function of converting triplet excitation energy into singlet excitation energy by up-conversion (pathway a in fig. 4A) 10). Therefore, the singlet excitation energy possessed by the compound 133 can be rapidly transferred to the compound 132 (pathway A in FIG. 4A)11). In this case, it is preferable to satisfy SC3≥SG。
Therefore, similarly to the above-described structural example 3, in the light-emitting layer 113 of the light-emitting device shown in this structural example, there is a path a through which triplet excitation energy passes in fig. 4A6A path to the path A8 to be transferred to the compound 132 as a guest material, and triplet excitation energy passing through the path a in fig. 4A10And route A11And to the pathway of compound 132. In this manner, the existence of a plurality of paths through which triplet excitation energy moves to the compound 132 which is a fluorescent substance can further improve light emission efficiency. On the path A8The exciplex is used as an energy donor and the compound 132 is used as an energy acceptor. On the path A11Compound 133 is used as an energy donor and compound 132 is used as an energy acceptor. However, in the light-emitting layer 113 of the light-emitting device shown in this structural example, there is a path (path a in fig. 4A) through which the triplet excitation energy of the exciplex is transferred to the T1 level of the compound 132, in addition to the above-described path9) There is a competition between the two. Where this energy transfer takes place (path A)9) In the case of (3), triplet excitation energy in the compound 132 which is a fluorescent light-emitting substance does not contribute to light emission, and thus the light-emitting efficiency of the light-emitting device is lowered.
To suppress this energy transfer (path A)9) As described in the above structural example 1, it is important that the distance between the exciplex formed from the compound 131 and the compound 133 and the compound 132, that is, the distance between the exciplex formed from the compound 131 and the compound 133 and the light-emitting substance contained in the compound 132 is long.
A part of the structure of the compound according to one embodiment of the present invention includes a light-emitting body and a protecting group, and when the compound is used as an energy acceptor in the light-emitting layer 113, the protecting group has a function of increasing the distance between an energy donor and the light-emitting body. Thus, when a compound according to one embodiment of the present invention is used as the compound 132, the concentration of the compound 132 can be increasedThe distance between the compound 132 and the exciplex formed from the compound 131 and the compound 133 can increase the energy transfer rate based on the forster mechanism while suppressing the energy transfer based on the dexter mechanism. Therefore, when a compound according to one embodiment of the present invention is used as the compound 132, the energy level of S1 (S) from the exciplex to the compound 132 is one aspectG) Transfer of triplet excitation energy (pathway A)6And route A8) And the S1 energy level (S) from the exciplex to compound 132 G) Transfer of triplet excitation energy (pathway A)10And route A11) On the other hand, the energy level T1 (T) from the exciplex to compound 132 is easily generatedG) Transfer of triplet excitation energy (pathway A)9: energy transfer based on the dexter mechanism) is suppressed, whereby the accompanying path a can be suppressed9The light emitting efficiency of the light emitting device is improved while the light emitting efficiency of the energy transfer is reduced.
< example 5 of Structure of light emitting layer >
This structural example shows the following case: the light-emitting layer 113 in the light-emitting device contains four substances, i.e., a compound 131, a compound 132, a compound 133, and a compound 134; as the compound 133, a substance having a function of converting triplet excitation energy into light emission, that is, a phosphorescent substance is used; the compound 131 and the compound 134 are a combination which forms an exciplex, and a fluorescent light-emitting substance is used as the compound 132 which serves as a light-emitting substance (guest material). Therefore, a compound according to one embodiment of the present invention is preferably used as the compound 132 which is a fluorescent substance. Fig. 4B shows an example of energy level correlation in the light-emitting layer 113 of the present structural example. The symbols and signs in fig. 4B are the same as those in fig. 3B, and the symbols and signs different from those in fig. 3B are given below.
·SC4: s1 energy level of compound 134
·TC4: t1 energy level of Compound 134
In this structural example, compound 131 and compound 134 form an exciplex. The S1 energy level (S) of the exciplexE) T1 level (T) of exciplexE) Adjacent energy levels (see path A in FIG. 4B)12). However, when an exciplex formed by utilizing two substances through the above-mentioned route loses excitation energy, the two substances exist as the original two substances, respectively.
Excitation level (S) of exciplexEAnd TE) The energy level (S) of S1 is higher than that of each of the exciplex-forming substances (Compound 131 and Compound 134)C1And SC4) Low, excited states can be formed with lower excitation energy. Thereby, the driving voltage of the light emitting device can be reduced.
In addition, since the compound 133 is a phosphorescent material, intersystem crossing between a singlet state and a triplet state is allowed. This enables both singlet excitation energy and triplet excitation energy of the exciplex to be rapidly transferred to the compound 133 (route a)13). In this case, T is preferably satisfiedE≥TC3。
Further, the triplet excitation energy of the compound 133 can be efficiently converted into the singlet excitation energy of the compound 132 (pathway a)14). Here, as shown in FIG. 4B, at TE≥TC3≥SGIn the case of (2), the excitation energy of the compound 133 is preferably transferred to the compound 132 as a guest material efficiently as singlet excitation energy. Specifically, it is preferable that a line is drawn at the end of the compound 133 on the short wavelength side of the phosphorescence spectrum, and the energy of the extrapolated wavelength is T C3The energy of the wavelength at the absorption edge of the absorption spectrum of the compound 132 is set to SGAt this time, TC is satisfied3≥SG. On the path A14Compound 133 is used as an energy donor and compound 132 is used as an energy acceptor.
In this case, the combination of the compound 131 and the compound 134 may be any combination as long as it can form an exciplex, and it is preferable that one of them is a compound having a hole-transporting property and the other is a compound having an electron-transporting property.
Further, as a combination of materials which efficiently form an exciplex, it is preferable that one of the compound 131 and the compound 134 has a higher HOMO level than the other, and that one has a higher LUMO level than the other.
Further, the energy level correlation of the compound 131 and the compound 134 is not limited to that shown in fig. 4B. That is, the singlet excitation level (S) of the compound 131C1) Can be higher than the singlet excitation level (S) of compound 134C4) Or below the singlet excitation level (S) of compound 134C4). Further, the triplet excitation level (T) of the compound 131C1) Can be higher than the triplet excitation level (T) of compound 134C4) Or below the triplet excitation level (T) of compound 134C4)。
In the light-emitting element according to one embodiment of the present invention, the compound 131 preferably has a pi-electron deficient skeleton. By adopting this structure, the LUMO level of compound 131 becomes low, which is suitable for exciplex formation.
In the light-emitting element according to one embodiment of the present invention, the compound 131 preferably has a pi-electron-rich skeleton. By adopting this structure, the HOMO level of compound 131 becomes high, which is suitable for the formation of exciplex.
A part of the structure of the compound according to one embodiment of the present invention includes a light-emitting body and a protecting group, and when the compound is used as an energy acceptor in the light-emitting layer 113, the protecting group has a function of increasing the distance between an energy donor and the light-emitting body. Thus, when a compound according to one embodiment of the present invention is used as the compound 132, the distance between the compound 133 and the compound 132 can be increased. Therefore, by using a compound of one embodiment of the present invention as the compound 132, on the one hand, the S1 energy level (S) from the compound 133 to the compound 132G) Transfer of triplet excitation energy (pathway A)14) Easily occurs, on the other hand, from the T1 level (T) of compound 133 to compound 132G) Transfer of triplet excitation energy (pathway A)15: energy transfer based on the dexter mechanism) is suppressed, whereby the accompanying path a can be suppressed15The light emitting efficiency of the light emitting device is improved while the light emitting efficiency of the energy transfer is reduced.
Further, in the present structural example, in the case of increasing the concentration of the compound 132, it is also possible to increase the energy transfer rate based on the ford mechanism while suppressing the energy transfer based on the dexter mechanism. By increasing the energy transfer rate based on the forster mechanism, the excitation lifetime of the energy acceptor in the light-emitting layer becomes short, and thus the reliability of the light-emitting device can be improved. Specifically, the concentration of the compound 132 in the light-emitting layer 113 is preferably 2 wt% or more and 50 wt% or less, more preferably 5 wt% or more and 30 wt% or less, and further preferably 5 wt% or more and 20 wt% or less, with respect to the compound 133 as an energy donor.
In this specification, the path a may be defined as12To A13The process of (2) is called EXTET (exact-Triplet Energy Transfer). In other words, in the light-emitting layer 113 in the present specification, supply of excitation energy from the exciplex to the compound 133 is generated.
< example 6 of Structure of light emitting layer >
This structural example shows the following case: the light-emitting layer 113 in the light-emitting device contains four substances, i.e., a compound 131, a compound 132, a compound 133, and a compound 134; as the compound 133, a substance having a function of converting triplet excitation energy into light emission, that is, a phosphorescent substance is used; the compound 131 and the compound 134 are a combination which forms an exciplex, and a fluorescent light-emitting substance is used as the compound 132 which serves as a light-emitting substance (guest material). Therefore, a compound according to one embodiment of the present invention is preferably used as the compound 132 which is a fluorescent substance. Further, the difference from the above structural example 5 is that the compound 134 is a material having TADF properties. Further, fig. 4C shows an example of energy level correlation in the light-emitting layer 113 of the present structural example. The explanation of the reference numerals and symbols in fig. 4C is omitted because they are the same as those in fig. 3B and 4B.
Here, the compound 134 is a TADF material. Therefore, the compound 134 which does not form an exciplex has a function of converting triplet excitation energy into singlet excitation energy by up-conversion (pathway a in fig. 4C)16). Therefore, the singlet excitation energy possessed by compound 134 can be rapidly transferred to compound 132 (pathway A in FIG. 4C)17). In this case, it is preferable to satisfy SC4≥SG. Specifically, it is preferable that compound 13 is4, the tail of the fluorescence spectrum on the short wavelength side is cut off, and the energy of the extrapolated wavelength is set to SC4Energy at the wavelength of the absorption edge of the absorption spectrum of the compound 132 or the tail of the short-wavelength side of the fluorescence spectrum of the compound 132 is cut off, and energy at the wavelength of the extrapolation line is set to SGAt this time, S is satisfiedC4≥SG。
Therefore, similarly to the above-described structural example 5, in the light-emitting layer 113 of the light-emitting device shown in this structural example, there is a path a through which triplet excitation energy passes in fig. 4C12To path A14And the path transferred to the compound 132 as a guest material and the triplet excitation energy pass through the path a in fig. 4C16And route A17And to the pathway of compound 132. In this manner, the existence of a plurality of paths through which triplet excitation energy moves to the compound 132 which is a fluorescent substance can further improve light emission efficiency. On the path A 14Compound 133 is used as an energy donor and compound 132 is used as an energy acceptor. On the path A17Compound 134 is used as an energy donor and compound 132 is used as an energy acceptor. However, in the light-emitting layer 113 of the light-emitting device shown in this structural example, in addition to the above, there is a path (path a in fig. 4C) through which the triplet excitation energy of the compound 133 is transferred to the T1 level of the compound 13215) There is a competition between the two. Where this energy transfer takes place (path A)15) In the case of (3), triplet excitation energy in the compound 132 which is a fluorescent light-emitting substance does not contribute to light emission, and thus the light-emitting efficiency of the light-emitting device is lowered.
To suppress this energy transfer (path A)15) As illustrated in the above structural example 1, it is important that the distance between the compound 133 and the compound 132, that is, the distance between the compound 133 and the light-emitting body included in the compound 132 is long.
A part of the structure of the compound according to one embodiment of the present invention includes a light-emitting body and a protecting group, and when the compound is used as an energy acceptor in the light-emitting layer 113, the protecting group has a function of increasing the distance between an energy donor and the light-emitting body. Thus, a compound of one embodiment of the present invention is used When the compound 132 is used as the compound 132, the distance between the compound 133 and the compound 132 can be increased even when the concentration of the compound 132 is increased, and the energy transfer rate based on the fox mechanism can be increased while the energy transfer based on the dexter mechanism is suppressed. Therefore, when a compound according to one embodiment of the present invention is used as the compound 132, the energy level of S1 (S) from the exciplex to the compound 132 is one aspectG) Transfer of triplet excitation energy (pathway A)12To path A14) And the S1 energy level (S) from the exciplex to compound 132G) Transfer of triplet excitation energy (pathway A)16And route A17) On the other hand, the T1 level (T) from the compound 133 to the compound 132 is easy to occurG) Transfer of triplet excitation energy (pathway A)15: energy transfer based on the dexter mechanism) is suppressed, whereby the accompanying path a can be suppressed15The light emitting efficiency of the light emitting device is improved while the light emitting efficiency of the energy transfer is reduced.
< structural example 7 of light-emitting layer >
This structural example shows the following case: the light-emitting layer 113 in the light-emitting device contains a compound 131, a compound 132, and a compound 133; as the compound 133, a substance having a function of converting triplet excitation energy into light emission, that is, a phosphorescent substance is used; as the compound 132 serving as a light-emitting substance (guest material), a fluorescent light-emitting substance is used. Therefore, a compound according to one embodiment of the present invention is preferably used as the compound 132 which is a fluorescent substance. The graph SA shows an example of energy level correlation in the light-emitting layer 113 of the present structural example. The labels and symbols in fig. 5A are listed below.
Comp (131): compound 131
Comp (133): compound 133
Guest (132): compound 132
·SC1: s1 energy level of Compound 131
·TC1: t1 energy level of Compound 131
·TC3: t1 level of Compound 133
·TG: t1 level of Compound 132
·SG: s1 energy level of Compound 132
In the present structural example, since recombination of carriers mainly occurs in the compound 131, singlet excitons and triplet excitons are generated. By selecting to satisfy TC3≤TC1The phosphorescent substance having the above relationship is a compound 133, and both singlet excitation energy and triplet excitation energy generated in the compound 131 can be transferred to T of the compound 133C3Energy level (Path A in FIG. 5A)18). Note that a part of the carriers is likely to be recombined in the compound 133.
The phosphorescent substance used in the above structure preferably contains heavy atoms such as Ir, Pt, Os, Ru, and Pd. When a phosphorescent substance is used as the compound 133, energy transfer from a triplet excitation level of an energy donor to a singlet excitation level of a guest material (energy acceptor) is allowed, and therefore, it is preferable. Therefore, the triplet excitation energy of compound 133 can be transmitted through pathway a19Transferred to the S1 energy level (S) of the guest materialG). On the path A19Compound 133 is used as an energy donor and compound 132 is used as an energy acceptor. At this time, T is satisfied C3≥SGIn the case of (3), excitation of the compound 133 is preferably transferred to a singlet excited state of the compound 132 as a guest material with high efficiency. Specifically, it is preferable that a line is drawn at the end of the compound 133 on the short wavelength side of the phosphorescence spectrum, and the energy of the extrapolated wavelength is TC3The energy of the wavelength at the absorption edge of the absorption spectrum of the compound 132 is set to SGAt this time, T is satisfiedC3≥SG. However, in the light-emitting layer 113 of the light-emitting device shown in this structural example, in addition to the above, there is a path (path a in fig. 5A) through which the triplet excitation energy of the compound 133 is transferred to the T1 level of the compound 13220) There is a competition between the two. Where this energy transfer takes place (path A)20) In the case of (3), triplet excitation energy in the compound 132 which is a fluorescent light-emitting substance does not contribute to light emission, and thus the light-emitting efficiency of the light-emitting device is lowered.
To suppress this energy transfer (path A)20) As illustrated in the above structural example 1, it is important that the distance between the compound 133 and the compound 132, that is, the distance between the compound 133 and the light-emitting body included in the compound 132 is long.
A part of the structure of the compound according to one embodiment of the present invention includes a light-emitting body and a protecting group, and when the compound is used as an energy acceptor in the light-emitting layer 113, the protecting group has a function of increasing the distance between an energy donor and the light-emitting body. Thus, when a compound according to one embodiment of the present invention is used as the compound 132, the distance between the compound 133 and the compound 132 can be increased even when the concentration of the compound 132 is increased, and the energy transfer rate by the fox mechanism can be increased while suppressing the energy transfer by the dexter mechanism. Therefore, by using a compound of one embodiment of the present invention as the compound 132, on the one hand, the S1 energy level (S) from the compound 133 to the compound 132 G) Transfer of triplet excitation energy (pathway A)19) Easily occurs, on the other hand, from the T1 level (T) of compound 133 to compound 132G) Transfer of triplet excitation energy (pathway A)20: energy transfer based on the dexter mechanism) is suppressed, whereby the accompanying path a can be suppressed20The light emitting efficiency of the light emitting device is improved while the light emitting efficiency of the energy transfer is reduced.
< example 8 of Structure of light emitting layer >
This structural example shows the following case: the light-emitting layer 113 in the light-emitting device contains a compound 131, a compound 132, and a compound 133; as the compound 133, a substance having a function of converting triplet excitation energy into light emission, that is, a material having TADF properties; as the compound 132 serving as a light-emitting substance (guest material), a fluorescent light-emitting substance is used. Therefore, a compound according to one embodiment of the present invention is preferably used as the compound 132 which is a fluorescent substance. Fig. 5B shows an example of energy level correlation in the light-emitting layer 113 of the present structural example. The symbols and symbols in fig. 5B are the same as those in fig. 5A, and the symbols and symbols different from those in fig. 5A are given below.
·SC3: s1 level of Compound 133
In the present structural example, becauseSince recombination of carriers mainly occurs in the compound 131, singlet excitons and triplet excitons are generated. Satisfies S by selection C3≤SC1And TC3≤TC1The TADF-related material of the compound (133) can transfer both singlet excitation energy and triplet excitation energy generated in the compound (131) to S of the compound (133)C3And TC3Energy level (Path A in FIG. 5B21). Note that a part of the carriers is likely to be recombined in the compound 133.
Compound 133 is a material in the TADF. Therefore, the compound 131 has a function of converting triplet excitation energy into singlet excitation energy by up-conversion (pathway a in fig. 5B)22). Further, the singlet excitation energy possessed by the compound 133 can be rapidly transferred to the compound 132 (path a in fig. 5B)23). In this case, it is preferable to satisfy SC3≥SG. Specifically, it is preferable that a tangent is drawn at the tail on the short-wavelength side of the emission spectrum of the exciplex using heavy atoms, and the energy of the extrapolated wavelength is set to SC3The energy of the wavelength at the absorption edge of the absorption spectrum of the compound 132 is set to SGAt this time, S is satisfiedC3≥SG。
Therefore, in the light-emitting layer 113 of the light-emitting device shown in this structural example, the light-emitting device was obtained by passing through the path a in fig. 5B21Route A22And route A23The triplet excitation energy generated in the compound 133 can be converted into fluorescence of the compound 132. On the path A 23Compound 133 is used as an energy donor and compound 132 is used as an energy acceptor. However, in the light-emitting layer 113 of the light-emitting device shown in this structural example, in addition to the above, there is a path (path a in fig. 5B) through which the triplet excitation energy generated in the compound 133 is transferred to the T1 level of the compound 13224) There is a competition between the two. Where this energy transfer takes place (path A)24) In the case of (3), triplet excitation energy in the compound 132 which is a fluorescent light-emitting substance does not contribute to light emission, and thus the light-emitting efficiency of the light-emitting device is lowered.
To suppress this energy transfer (path A)24) As illustrated in the above structural example 1, it is important that the distance between the compound 133 and the compound 132, that is, the distance between the compound 133 and the light-emitting body included in the compound 132 is long.
A part of the structure of the compound according to one embodiment of the present invention includes a light-emitting body and a protecting group, and when the compound is used as an energy acceptor in the light-emitting layer 113, the protecting group has a function of increasing the distance between an energy donor and the light-emitting body. Thus, when a compound according to one embodiment of the present invention is used as the compound 132, the distance between the compound 133 and the compound 132 can be increased even when the concentration of the compound 132 is increased, and the energy transfer rate by the fox mechanism can be increased while suppressing the energy transfer by the dexter mechanism. Therefore, by using a compound of one embodiment of the present invention as the compound 132, on the one hand, the S1 energy level (S) from the compound 133 to the compound 132 G) Transfer of triplet excitation energy (pathway A)23) Easily occurs, on the other hand, from the T1 level (T) of compound 133 to compound 132G) Transfer of triplet excitation energy (pathway A)24: energy transfer based on the dexter mechanism) is suppressed, whereby the accompanying path a can be suppressed24The light emitting efficiency of the light emitting device is improved while the light emitting efficiency of the energy transfer is reduced.
Embodiment 3
In this embodiment mode, a light-emitting device according to one embodiment of the present invention is described.
Structure of light emitting device
Fig. 6A and 6B illustrate an example of a light-emitting device including an EL layer having a light-emitting layer between a pair of electrodes. Specifically, the EL layer 103 is interposed between the first electrode 101 and the second electrode 102. For example, when the first electrode 101 is used as an anode, the EL layer 103 has a structure in which a hole injection layer 111, a hole transport layer 112, a light-emitting layer 113, an electron transport layer 114, and an electron injection layer 115 are sequentially stacked as functional layers. Further, the light-emitting layer 113 includes a host material using the third organic compound 123 and a guest material using the first organic compound 121 as a material having a function of converting singlet excitation energy into light emission (a fluorescent substance) and the second organic compound 122 as a material having a function of converting triplet excitation energy into light emission (a phosphorescent substance or a TADF material).
As other structures of the light-emitting device, a light-emitting device which can be driven at a low voltage by having a structure including a plurality of EL layers formed so as to sandwich a charge generation layer between a pair of electrodes (a series structure), a light-emitting device which improves optical characteristics by forming an optical microcavity resonator (microcavity) structure between a pair of electrodes, and the like are also included in one embodiment of the present invention. The charge generation layer has the following functions: a function of injecting electrons into one of the adjacent EL layers and injecting holes into the other EL layer when a voltage is applied to the first electrode 101 and the second electrode 102.
At least one of the first electrode 101 and the second electrode 102 of the light-emitting device is an electrode having light-transmitting properties (e.g., a transparent electrode, a semi-transmissive and semi-reflective electrode). When the electrode having light transmittance is a transparent electrode, the visible light transmittance of the transparent electrode is 40% or more. In the case where the electrode is a semi-transmissive and semi-reflective electrode, the visible light reflectance of the semi-transmissive and semi-reflective electrode is 20% or more and 80% or less, and preferably 40% or more and 70% or less. Further, the resistivity of these electrodes is preferably 1 × 10-2Omega cm or less.
In the light-emitting device according to the above-described one embodiment of the present invention, when one of the first electrode 101 and the second electrode 102 is a reflective electrode (reflective electrode), the visible light reflectance of the reflective electrode is 40% or more and 100% or less, and preferably 70% or more and 100% or less. Further, the resistivity of the electrode is preferably 1 × 10-2Omega cm or less.
< first electrode and second electrode >
As materials for forming the first electrode 101 and the second electrode 102, the following materials may be appropriately combined if the functions of the two electrodes can be satisfied. For example, metals, alloys, conductive compounds, mixtures thereof, and the like can be suitably used. Specific examples thereof include an In-Sn oxide (also referred to as ITO), an In-Si-Sn oxide (also referred to as ITSO), an In-Zn oxide, and an In-W-Zn oxide. In addition to the above, metals such as aluminum (Al), titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), gallium (Ga), zinc (Zn), indium (In), tin (Sn), molybdenum (Mo), tantalum (Ta), tungsten (W), palladium (Pd), gold (Au), platinum (Pt), silver (Ag), yttrium (Y), neodymium (Nd), and alloys appropriately combining these metals may be mentioned. In addition to the above, elements belonging to group 1 or group 2 of the periodic table (for example, rare earth metals such as lithium (Li), cesium (Cs), calcium (Ca), strontium (Sr)), europium (Eu), ytterbium (Yb), etc., alloys in which these are appropriately combined, graphene, and the like can be used.
Note that these electrodes can be formed by a sputtering method or a vacuum evaporation method.
< hole injection layer >
The hole injection layer 111 is a layer for injecting holes from the first electrode 101 of the anode into the EL layer 103, and includes an organic acceptor material and a material having a high hole-injecting property.
The organic acceptor material can generate holes in an organic compound by charge separation from other organic compounds whose HOMO level has a value close to that of the LUMO level. Therefore, as the organic acceptor material, a compound having an electron-withdrawing group (halogen group or cyano group) such as a quinodimethane derivative, a tetrachlorobenzoquinone derivative, or a hexaazatriphenylene derivative can be used. For example, 7, 8, 8-tetracyano-2, 3, 5, 6-tetrafluoroquinodimethane (abbreviated as F) can be used4-TCNQ), 3, 6-difluoro-2, 5, 7, 7, 8, 8-hexacyano-p-quinodimethane, chloranil, 2, 3, 6, 7, 10, 11-hexacyan-1, 4, 5, 8, 9, 12-hexaazatriphenylene (abbreviation: HAT-CN), 1, 3, 4, 5, 7, 8-hexafluorotetracyano (hexafluoroacetonitrile) -naphthoquinone dimethane (naphthoquinodimethane) (abbreviation: F6-TCNNQ), and the like. Among the organic acceptor materials, HAT-CN is particularly preferable because it has a high acceptor property and the film quality is thermally stable. Further, [3 ] ]The axine derivative is particularly preferable because it has a very high electron-accepting property. Specifically, it is possible to use: alpha, alpha' -1, 2, 3-cyclopropane triylidene tris [ 4-cyano-2, 3, 5, 6-tetrafluorophenylacetonitrile]、α，α′，α″-1，2, 3-Cyclopropanetriylidenetris [2, 6-dichloro-3, 5-difluoro-4- (trifluoromethyl) benzeneacetonitrile]Alpha, alpha' -1, 2, 3-cyclopropane triylidenetris [2, 3, 4, 5, 6-pentafluorophenylacetonitrile]And the like.
Examples of the material having a high hole-injecting property include transition metal oxides such as molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, and manganese oxide. In addition to the above, phthalocyanine-based compounds such as phthalocyanine (abbreviated as H) can be used2Pc), copper phthalocyanine (CuPc), and the like.
Further, aromatic amine compounds of low-molecular compounds such as 4, 4 '-tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4' -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), 4 '-bis [ N- (4-diphenylaminophenyl) -N-phenylamino ] biphenyl (abbreviated as DPAB), 4' -bis (N- {4- [ N '- (3-methylphenyl) -N' -phenylamino ] phenyl } -N-phenylamino) biphenyl (abbreviated as DNTPD), 1, 3, 5-tris [ N- (4-diphenylaminophenyl) -N-phenylamino ] benzene (abbreviated as DPA3B), and the like can be used, 3- [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviation: PCzPCA1), 3, 6-bis [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviation: PCzPCA2), 3- [ N- (1-naphthyl) -N- (9-phenylcarbazol-3-yl) amino ] -9-phenylcarbazole (abbreviation: PCzPCN1), and the like.
In addition, high molecular compounds (oligomers, dendrimers or polymers) such as Poly (N-vinylcarbazole) (abbreviated as PVK), Poly (4-vinyltriphenylamine) (abbreviated as PVTPA), Poly [ N- (4- { N '- [4- (4-diphenylamino) phenyl ] phenyl-N' -phenylamino } phenyl) methacrylamide ] (abbreviated as PTPDMA), Poly [ N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine ] (abbreviated as Poly-TPD) and the like can be used. Alternatively, a polymer compound to which an acid is added, such as poly (3, 4-ethylenedioxythiophene)/poly (styrenesulfonic acid) (abbreviated as PEDOT/PSS) or polyaniline/poly (styrenesulfonic acid) (PANI/PSS), may also be used.
As the material having a high hole-injecting property, a composite material including a hole-transporting material and an acceptor material (electron acceptor material) may be used. In this case, electrons are extracted from the hole-transporting material by the acceptor material to generate holes in the hole injection layer 111, and the holes are injected into the light-emitting layer 113 through the hole-transporting layer 112. The hole injection layer 111 may be a single layer made of a composite material including a hole-transporting material and an acceptor material (electron acceptor material), or may be a stack of layers formed using a hole-transporting material and an acceptor material (electron acceptor material).
The hole-transporting material preferably has a molecular weight of 1X 10-6cm2A substance having a hole mobility of greater than/Vs. In addition, any substance other than the above may be used as long as it has a hole-transporting property higher than an electron-transporting property.
The hole-transporting material is preferably a material having high hole-transporting property, such as a pi-electron-rich heteroaromatic compound (e.g., a carbazole derivative or a furan derivative) or an aromatic amine (a compound having an aromatic amine skeleton).
Examples of the carbazole derivative (compound having a carbazole skeleton) include a biscarbazole derivative (for example, 3, 3' -biscarbazole derivative), an aromatic amine having a carbazole group, and the like.
Specific examples of the bicarbazole derivative (for example, 3, 3 '-bicarbazole derivative) include 3, 3' -bis (9-phenyl-9H-carbazole) (abbreviated as PCCP), 9 '-bis (1, 1' -biphenyl-4-yl) -3, 3 '-bi-9H-carbazole, 9' -bis (1, 1 '-biphenyl-3-yl) -3, 3' -bi-9H-carbazole, 9- (1, 1 '-biphenyl-3-yl) -9' - (1, 1 '-biphenyl-4-yl) -9H, 9' H-3, 3 '-bicarbazole (abbreviated as mBPCCBP), and 9- (2-naphthyl) -9' -phenyl-9H, 9 'H-3, 3' -bicarbazole (abbreviated as. beta. NCCP), and the like.
Specific examples of the aromatic amine having the carbazole group include 4-phenyl-4 '- (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated to PCBA1BP), N- (4-biphenyl) -N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-phenyl-9H-carbazol-3-amine (abbreviated to pcsif), N- (1, 1' -biphenyl-4-yl) -N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl ] -9, 9-dimethyl-9H-fluoren-2-amine (abbreviated to PCBBiF), 4, 4 ' -diphenyl-4 ' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated as PCBBi1BP), 4- (1-naphthyl) -4 ' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated as PCBANB), 4 ' -di (1-naphthyl) -4 ' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated as PCBNBB), 4-phenyldiphenyl- (9-phenyl-9H-carbazol-3-yl) amine (abbreviated as PCA1BP), N ' -bis (9-phenylcarbazol-3-yl) -N, N ' -diphenylbenzene-1, 3-diamine (PCA 2B), N ' -triphenyl-N, N ' -tris (9-phenylcarbazol-3-yl) benzene-1, 3, 5-triamine (PCA 3B), 9-dimethyl-N-phenyl-N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl ] fluorene-2-amine (PCBAF), N-phenyl-N- [4- (9-phenyl-9H-carbazol-3-yl) phenyl ] spiro-9, 9 ' -bifluorene-2-amine (PCBASF), 3- [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] -9-phenylcarbazole (PCA 1), 3, 6-bis [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] -9-phenylcarbazole (abbreviation: PCzPCA2), 3- [ N- (1-naphthyl) -N- (9-phenylcarbazol-3-yl) amino ] -9-phenylcarbazole (abbreviation: PCzPCN1), 3- [ N- (4-diphenylaminophenyl) -N-phenylamino ] -9-phenylcarbazole (abbreviation: PCzDPA1), 3, 6-bis [ N- (4-diphenylaminophenyl) -N-phenylamino ] -9-phenylcarbazole (abbreviation: PCzDPA2), 3, 6-bis [ N- (4-diphenylaminophenyl) -N- (1-naphthyl) amino ] -9-phenylcarbazole (abbreviation: PCzTPN2) ) 2- [ N- (9-phenylcarbazol-3-yl) -N-phenylamino ] spiro-9, 9' -bifluorene (abbreviation: PCASF), N- [4- (9H-carbazol-9-yl) phenyl ] -N- (4-phenyl) phenylaniline (abbreviation: YGA1BP), N '-bis [4- (carbazol-9-yl) phenyl ] -N, N' -diphenyl-9, 9-dimethylfluorene-2, 7-diamine (abbreviation: YGA2F), 4', 4 ″ -tris (carbazol-9-yl) triphenylamine (abbreviation: TCTA), and the like.
As the carbazole derivative, in addition to the above, examples thereof include 3- [4- (9-phenanthryl) -phenyl ] -9-phenyl-9H-carbazole (abbreviated as PCPPn), 3- [4- (1-naphthyl) -phenyl ] -9-phenyl-9H-carbazole (abbreviated as PCPN), 1, 3-bis (N-carbazolyl) benzene (abbreviated as mCP), 4' -bis (N-carbazolyl) biphenyl (abbreviated as CBP), 3, 6-bis (3, 5-diphenylphenyl) -9-phenylcarbazole (abbreviated as CZTP), 1, 3, 5-tris [4- (N-carbazolyl) phenyl ] benzene (abbreviated as TCPB), 9- [4- (10-phenyl-9-anthracyl) phenyl ] -9H-carbazole (abbreviated as CZPA) and the like.
Specific examples of the furan derivative (compound having a furan skeleton) include compounds having a thiophene skeleton such as 4 ', 4 ' - (benzene-1, 3, 5-triyl) tris (dibenzothiophene) (abbreviated as DBT3P-II), 2, 8-diphenyl-4- [4- (9-phenyl-9H-fluoren-9-yl) phenyl ] dibenzothiophene (abbreviated as DBTFLP-III), 4- [4- (9-phenyl-9H-fluoren-9-yl) phenyl ] -6-phenyldibenzothiophene (abbreviated as DBTFLP-IV), and 4, 4 ' - (benzene-1, 3, 5-triyl) tris (dibenzofuran) (abbreviated as DBF3P-II), 4- {3- [3- (9-phenyl-9H-fluoren-9-yl) phenyl ] phenyl } dibenzofuran (mmDBFFLBi-II).
Specific examples of the aromatic amine include 4, 4 ' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (abbreviated as NPB or. alpha. -NPD), N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1, 1 ' -biphenyl ] -4, 4 ' -diamine (abbreviated as TPD), 4 ' -bis [ N- (spiro-9, 9 ' -difluoren-2-yl) -N-phenylamino ] biphenyl (abbreviated as BSPB), 4-phenyl-4 ' - (9-phenylfluoren-9-yl) triphenylamine (abbreviated as BPAFLP), 4-phenyl-3 ' - (9-phenylfluoren-9-yl) triphenylamine (abbreviated as mBPAFLP), N- (9, 9-dimethyl-9H-fluoren-2-yl) -N- {9, 9-dimethyl-2- [ N ' -phenyl-N ' - (9, 9-dimethyl-9H-fluoren-2-yl) amino ] -9H-fluoren-7-yl } phenylamine (abbreviated: DFLADFL), N- (9, 9-dimethyl-2-diphenylamino-9H-fluoren-7-yl) diphenylamine (abbreviated: DPNF), 2- [ N- (4-diphenylaminophenyl) -N-phenylamino ] spiro-9, 9 ' -bifluorene (abbreviated: DPASF), 2, 7-bis [ N- (4-diphenylaminophenyl) -N-phenylamino ] -spiro-9, 9 ' -dibenzofuran (abbreviation: DPA2SF), 4 ' -tris [ N- (1-naphthyl) -N-phenylamino ] triphenylamine (abbreviation: 1 ' -TNATA), 4 ' -tris (N, N-diphenylamino) triphenylamine (abbreviation: TDATA), 4 ' -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviation: m-MTDATA), N ' -bis (p-tolyl) -N, N ' -diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4 ' -bis [ N- (4-diphenylaminophenyl) -N-phenylamino ] biphenyl (abbreviation: DPAB), N ' -bis {4- [ bis (3-methylphenyl) amino ] phenyl } -N, n ' -diphenyl- (1, 1 ' -biphenyl) -4, 4 ' -diamine (abbreviated as DNTPD), 1, 3, 5-tris [ N- (4-diphenylaminophenyl) -N-phenylamino ] benzene (abbreviated as DPA3B), and the like.
As the hole transporting material, a polymer compound such as Poly (N-vinylcarbazole) (abbreviated as PVK), Poly (4-vinyltriphenylamine) (abbreviated as PVTPA), Poly [ N- (4- { N '- [4- (4-diphenylamino) phenyl ] phenyl-N' -phenylamino } phenyl) methacrylamide ] (abbreviated as PTPDMA), Poly [ N, N '-bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine ] (abbreviated as Poly-TPD) or the like can be used.
Note that the hole-transporting material is not limited to the above-described materials, and one or a combination of a plurality of known various materials may be used as the hole-transporting material.
As an acceptor material for the hole injection layer 111, an oxide of a metal belonging to groups 4 to 8 in the periodic table of elements can be used. Specific examples thereof include molybdenum oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, tungsten oxide, manganese oxide, and rhenium oxide. Molybdenum oxide is particularly preferably used because it is also stable in the atmosphere, has low hygroscopicity, and is easy to handle. In addition, the above organic acceptor materials may be used.
Note that the hole injection layer 111 can be formed by a known film formation method, for example, by a vacuum evaporation method.
< hole transport layer >
The hole transport layer 112 is a layer that transports holes injected from the first electrode 101 through the hole injection layer 111 into the light emitting layer 113. Further, the hole-transporting layer 112 is a layer containing a hole-transporting material. Therefore, as the hole transporting layer 112, a hole transporting material that can be used for the hole injecting layer 111 can be used.
Note that in the light-emitting device according to one embodiment of the present invention, the same organic compound as that used for the hole-transporting layer 112 is preferably used for the light-emitting layer 113. This is because: by using the same organic compound for the hole transport layer 112 and the light-emitting layer 113, holes are efficiently transported from the hole transport layer 112 to the light-emitting layer 113.
< light-emitting layer >
The light-emitting layer 113 is a layer containing a light-emitting substance. The light-emitting layer 113 in the light-emitting device according to one embodiment of the present invention includes a host material in which the third organic compound 123 is used, and a guest material in which the first organic compound 121 which is a material having a function of converting singlet excitation energy into light emission (a fluorescent substance) and the second organic compound 122 which is a material having a function of converting triplet excitation energy into light emission (a phosphorescent substance or a TADF material) are used. The light-emitting substance which can be used in the light-emitting layer 113 is not particularly limited as long as the above conditions are satisfied, and a substance which emits light of a color such as blue, violet, bluish violet, green, yellowish green, yellow, orange, or red can be used as appropriate.
As a host material used for the light-emitting layer 113, various organic compounds and exciplexes formed from these organic compounds can be used. Further, as the third organic compound 123 used as a host material, a substance having an energy gap larger than that of the first organic compound 121 or the second organic compound 122 used as a guest material is preferably used. Further, the lowest singlet excitation level (S1 level) of the third organic compound 123 is preferably higher than the S1 level of the first organic compound 121, and the lowest triplet excitation level (T1 level) of the third organic compound 123 is preferably higher than the T1 level of the first organic compound 121. Further, the lowest triplet excitation level (T1 level) of the third organic compound 123 is preferably higher than the T1 level of the second organic compound 122.
As the one or more kinds of organic compounds used as the host material, organic compounds such as a hole transport material which can be used for the above-described hole transport layer 112 and an electron transport material which can be used for the below-described electron transport layer 114 can be used as long as the conditions of the host material used for the light emitting layer are satisfied, and an exciplex formed of a plurality of materials can also be used. Further, an Exciplex (exiplex) which forms an excited state with a plurality of organic compounds has a function as a TADF material which can convert triplet excitation energy into singlet excitation energy because the difference between the S1 level and the T1 level is extremely small. As a combination of a plurality of organic compounds forming an exciplex, for example, it is preferable that one has a pi-electron deficient heteroaromatic ring and the other has a pi-electron rich heteroaromatic ring. In addition, as one of the combinations for forming the exciplex, a phosphorescent substance such as iridium, rhodium, a platinum-based organometallic complex, a metal complex, or the like may be used.
Further, the first organic compound 121 and the second organic compound 122 which are used as guest materials of the light-emitting layer 113 preferably exhibit different emission colors, respectively. Further, white light emission obtained by combining emission colors in a complementary color relationship may be used.
Further, a material having a function of converting singlet excitation energy into light emission, which is one guest material in the light-emitting layer 113, that is, the first organic compound 121 can use the material shown in embodiment mode 2 in a combination satisfying the conditions of the guest material used for the light-emitting layer. As the second organic compound 122, which is a material having a function of converting triplet excitation energy into light emission, as another guest material in the light-emitting layer 113, for example, a substance that emits phosphorescence (phosphorescent substance) or a Thermally Activated Delayed Fluorescence (TADF) material that exhibits Thermally activated delayed fluorescence can be used. These materials may also be used in a combination satisfying the conditions of the guest material for the light-emitting layer. Further, the lowest singlet excitation level (S1 level) of the first organic compound 121 is higher than the T1 level of the second organic compound 122. That is, the peak wavelength of the emission spectrum of the light emission obtained from the second organic compound 122 is longer than the light emission obtained from the first organic compound 121.
The phosphorescent material refers to a compound that emits phosphorescence without emitting fluorescence at any temperature in a temperature range of low temperature (e.g., 77K) or more and room temperature or less (i.e., 77K or more and 313K or less). The phosphorescent material preferably contains a metal element having a large spin-orbit interaction, and an organometallic complex, a metal complex (platinum complex), a rare earth metal complex, or the like can be used. Specifically, it preferably contains a transition metal element, particularly preferably contains a platinum group element (ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), or platinum (Pt)), and particularly preferably contains iridium. Iridium is preferable because it can increase the transition probability of a direct transition between the singlet ground state and the triplet excited state.
Examples of the phosphorescent substance exhibiting blue or green color and having an emission spectrum with a peak wavelength of 450nm to 570nm include the following substances.
For example, tris {2 }- [5- (2-methylphenyl) -4- (2, 6-dimethylphenyl) -4H-1, 2, 4-triazol-3-yl-. kappa.N2]Phenyl-kappa C iridium (III) (abbreviation: [ Ir (mpptz-dmp) ]3]) Tris (5-methyl-3, 4-diphenyl-4H-1, 2, 4-triazole) iridium (III) (abbreviation: [ Ir (Mptz)3]) Tris [4- (3-biphenyl) -5-isopropyl-3-phenyl-4H-1, 2, 4-triazole ]Iridium (III) (abbreviation: [ Ir (iPrptz-3b)3]) Tris [3- (5-biphenyl) -5-isopropyl-4-phenyl-4H-1, 2, 4-triazole]Iridium (III) (abbreviation: [ Ir (iPr5btz)3]) And organometallic complexes having a 4H-triazole skeleton; tris [ 3-methyl-1- (2-methylphenyl) -5-phenyl-1H-1, 2, 4-triazole]Iridium (III) (abbreviation: [ Ir (Mptz1-mp)3]) Tris (1-methyl-5-phenyl-3-propyl-1H-1, 2, 4-triazole) iridium (III) (abbreviation: [ Ir (Prptz1-Me)3]) And the like organometallic complexes having a 1H-triazole skeleton; fac-tris [1- (2, 6-diisopropylphenyl) -2-phenyl-1H-imidazole]Iridium (III) (abbreviation: [ Ir (iPrpmi)3]) Tris [3- (2, 6-dimethylphenyl) -7-methylimidazo [1, 2-f ]]Phenanthridino (phenanthrinato)]Iridium (III) (abbreviation: [ Ir (dmpimpt-Me)3]) And the like organic metal complexes having an imidazole skeleton; and bis [2- (4 ', 6' -difluorophenyl) pyridinato-N, C2′]Iridium (III) tetrakis (1-pyrazolyl) borate (FIr 6 for short), bis [2- (4 ', 6' -difluorophenyl) pyridinato-N, C2′]Iridium (III) picolinate (Firpic for short), bis {2- [3 ', 5' -bis (trifluoromethyl) phenyl]pyridinato-N, C2′Iridium (III) picolinate (abbreviation: [ Ir (CF)3ppy)2(pic)]) Bis [2- (4 ', 6' -difluorophenyl) pyridinato-N, C2′]Organometallic complexes in which an electron-withdrawing group-containing phenylpyridine derivative is a ligand, such as iridium (III) acetylacetonate (FIr (acac)).
The phosphorescent substance exhibiting green or yellow color and having an emission spectrum with a peak wavelength of 495nm or more and 590nm or less includes the following substances.
For example, tris (4-methyl-6-phenylpyrimidine) iridium (III) (abbreviation: [ Ir (mppm))3]) Tris (4-tert-butyl-6-phenylpyrimidine) iridium (III) (abbreviation: [ Ir (tBuppm)3]) (acetylacetonate) bis (6-methyl-4-phenylpyrimidine) iridium (III) (abbreviation)：[Ir(mppm)2(acac)]) And (acetylacetonate) bis (6-tert-butyl-4-phenylpyrimidine) iridium (III) (abbreviation: [ Ir (tBuppm)2(acac)]) (Acetylacetonate) bis [6- (2-norbornyl) -4-phenylpyrimidine]Iridium (III) (abbreviation: [ Ir (nbppm)2(acac)]) (Acetylacetonate) bis [ 5-methyl-6- (2-methylphenyl) -4-phenylpyrimidine]Iridium (III) (abbreviation: [ Ir (mpmppm))2(acac)]) And (acetylacetonate) bis {4, 6-dimethyl-2- [6- (2, 6-dimethylphenyl) -4-pyrimidinyl-. kappa.N3]Phenyl-. kappa.C } Iridium (III) (abbreviation: [ Ir (dmppm-dmp) ]2(acac)]) And (acetylacetonate) bis (4, 6-diphenylpyrimidine) iridium (III) (abbreviation: [ Ir (dppm)2(acac)]) And the like organometallic iridium complexes having a pyrimidine skeleton; (Acetylacetonato) bis (3, 5-dimethyl-2-phenylpyrazine) Iridium (III) (abbreviation: [ Ir (mppr-Me)2(acac)]) And (acetylacetonate) bis (5-isopropyl-3-methyl-2-phenylpyrazine) iridium (III) (abbreviation: [ Ir (mppr-iPr) 2(acac)]) And the like organometallic iridium complexes having a pyrazine skeleton; tris (2-phenylpyridinato-N, C)2′) Iridium (III) (abbreviation: [ Ir (ppy)3]) Bis (2-phenylpyridinato-N, C)2′) Iridium (III) acetylacetone (abbreviation: [ Ir (ppy)2(acac)]) Bis (benzo [ h ]]Quinoline) iridium (III) acetylacetone (abbreviation: [ Ir (bzq)2(acac)]) Tris (benzo [ h ]) or a salt thereof]Quinoline) iridium (III) (abbreviation: [ Ir (bzq)3]) Tris (2-phenylquinoline-N, C)2′) Iridium (III) (abbreviation: [ Ir (pq)3]) Bis (2-phenylquinoline-N, C)2′) Iridium (III) acetylacetone (abbreviation: [ Ir (pq)2(acac)]) Bis [2- (2-pyridyl-. kappa.N) phenyl-. kappa.C][2- (4-phenyl-2-pyridyl-. kappa.N) phenyl-. kappa.C]Iridium (III) (abbreviation: [ Ir (ppy)2(4dppy)]) Bis [2- (2-pyridyl-. kappa.N) phenyl-. kappa.C][2- (4-methyl-5-phenyl-2-pyridyl-. kappa.N) phenyl-. kappa.C]And the like organometallic iridium complexes having a pyridine skeleton; bis (2, 4-diphenyl-1, 3-oxazole-N, C2′) Iridium (III) acetylacetone (abbreviation: [ Ir (dpo)2(acac)]) Bis {2- [ 4' - (perfluorophenyl) phenyl]pyridine-N, C2′Iridium (III) acetylacetone (abbreviation [ Ir (p-PF-ph)2(acac)]) Bis (2-phenylbenzothiazole-N, C)2′) Iridium (III) acetylacetone (abbreviation: [ Ir (bt)2(acac)]) Isoorgano goldThe metal complex, tris (acetylacetonate) (monophenanthroline) terbium (III) (abbreviation: [ Tb (acac))3(Phen)]) And the like.
The phosphorescent substance exhibiting yellow or red color and having an emission spectrum with a peak wavelength of 570nm or more and 750nm or less includes the following substances.
For example, bis [4, 6-bis (3-methylphenyl) pyrimidino ] isobutyrylmethanoate]Iridium (III) (abbreviation: [ Ir (5mdppm)2(dibm)]) Bis [4, 6-bis (3-methylphenyl) pyrimidino radical](Dipivaloylmethane) Iridium (III) (abbreviation: [ Ir (5 mddppm)2(dpm)]) And (dipivaloylmethane) bis [4, 6-di (naphthalen-1-yl) pyrimidinium radical]Iridium (III) (abbreviation: [ Ir (d1npm)2(dpm)]) And the like organic metal complexes having a pyrimidine skeleton; (acetylacetonato) bis (2, 3, 5-triphenylpyrazine) iridium (III) (abbreviation: [ Ir (tppr))2(acac)]) Bis (2, 3, 5-triphenylpyrazine) (dipivaloylmethane) iridium (III) (abbreviation: [ Ir (tppr)2(dpm)]) Bis {4, 6-dimethyl-2- [3- (3, 5-dimethylphenyl) -5-phenyl-2-pyrazinyl-. kappa.N]Phenyl-kappa C } (2, 6-dimethyl-3, 5-heptanedione-kappa)2O, O') iridium (III) (abbreviation: [ Ir (dmdppr-P)2(dibm)]) Bis {4, 6-dimethyl-2- [5- (4-cyano-2, 6-dimethylphenyl) -3- (3, 5-dimethylphenyl) -2-pyrazinyl-. kappa.N]Phenyl- κ C } (2, 2, 6, 6-tetramethyl-3, 5-heptanedione- κ)2O, O') iridium (III) (abbreviation: [ Ir (dmdppr-dmCP)2(dpm)]) Bis [2- (5- (2, 6-dimethylphenyl) -3- (3, 5-dimethylphenyl) -2-pyrazinyl-. kappa.N) -4, 6-dimethylphenyl-. kappa.C ] ](2, 2, 6, 6-tetramethyl-3, 5-heptanedione-. kappa.2O, O') iridium (III) (abbreviation: [ Ir (dmdppr-dmp)2(dpm)]) (acetylacetone) bis [ 2-methyl-3-phenylquinoxalineato)]-N，C2′]Iridium (III) (abbreviation: [ Ir (mpq))2(acac)]) (acetylacetone) bis (2, 3-diphenylquinoxalineato) -N, C2′]Iridium (III) (abbreviation: [ Ir (dpq))2(acac)]) (acetylacetonato) bis [2, 3-bis (4-fluorophenyl) quinoxalato)]Iridium (III) (abbreviation: [ Ir (Fdpq)2(acac)]) And the like organic metal complexes having a pyrazine skeleton; tris (1-phenylisoquinoline-N, C)2′) Iridium (III) (abbreviation)：[Ir(piq)3]) Bis (1-phenylisoquinoline-N, C)2′) Iridium (III) acetylacetone (abbreviation: [ Ir (piq)2(acac)]) Bis [4, 6-dimethyl-2- (2-quinoline-. kappa.N) phenyl-. kappa.C](2, 4-Pentanedionato-. kappa.)2O, O') iridium (III) (abbreviation: [ Ir (dmpqn)2(acac)]) And the like organic metal complexes having a pyridine skeleton; 2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-porphyrin platinum (II) (abbreviation [ PtOEP ]]) And platinum complexes; and tris (1, 3-diphenyl-1, 3-propanedione (propanoiono)) (monophenanthroline) europium (III) (abbreviation: [ Eu (DBM))3(Phen)]) Tris [1- (2-thenoyl) -3, 3, 3-trifluoroacetone](Monophenanthroline) europium (III) (abbreviation: [ Eu (TTA))3(Phen)]) And the like.
As the TADF material, the following materials can be used. The TADF material is a material having a small energy difference (preferably 0.2eV or less) between the S1 level and the T1 level, and capable of converting (up-convert) a triplet excited state into a singlet excited state (inter-inversion cross) by a small amount of thermal energy and efficiently emitting light emission (fluorescence) from the singlet excited state. The conditions under which the thermally activated delayed fluorescence can be obtained with high efficiency are as follows: the energy difference between the triplet excitation level and the singlet excitation level is 0eV or more and 0.2eV or less, and preferably 0eV or more and 0.1eV or less. The delayed fluorescence emitted from the TADF material means luminescence having the same spectrum as that of general fluorescence but having a very long lifetime. Its life is 1X 10-6Second or more, preferably 1X 10-3For more than a second.
Examples of the TADF material include fullerene or a derivative thereof, an acridine derivative such as luteolin, and eosin. Further, metal-containing porphyrins containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), palladium (Pd), or the like can be cited. Examples of the metal-containing porphyrin include protoporphyrin-tin fluoride complex (abbreviated as SnF)2(Proto IX)), mesoporphyrin-tin fluoride complex (abbreviation: SnF 2(Meso IX)), hematoporphyrin-tin fluoride complex (abbreviation: SnF2(Hemato IX)), coproporphyrin tetramethyl ester-tin fluoride complex (abbreviation: SnF2(Copro III-4Me)), octaethylporphyrin-tin fluoride complex (abbreviation: SnF2(OEP)), protoporphyrin-tin fluoride complex (abbreviation: SnF2(Etio I)) and octaethylporphyrin-platinum chloride complex (abbreviation: PtCl2OEP), and the like.
[ chemical formula 24]
Figure BDA0002659073460000951
In addition to the above, 2- (biphenyl-4-yl) -4, 6-bis (12-phenylindolo [2, 3-a ] carbazol-11-yl) -1, 3, 5-triazine (abbreviation: PIC-TRZ), 2- {4- [3- (N-phenyl-9H-carbazol-3-yl) -9H-carbazol-9-yl ] phenyl } -4, 6-diphenyl-1, 3, 5-triazine (abbreviation: PCCzPTzn), 2- [4- (10H-phenoxazin-10-yl) phenyl ] -4, 6-diphenyl-1, 3, 5-triazine (abbreviation: PXZ-TRZ), 3- [4- (5-phenyl-5, 10-dihydrophenazin-10-yl) phenyl ] -4, 5-diphenyl-1, 2, 4-triazole (abbreviation: PPZ-3TPT), 3- (9, 9-dimethyl-9H-acridin-10-yl) -9H-xanthen-9-one (abbreviation: ACRXTN), bis [4- (9, 9-dimethyl-9, 10-dihydroacridine) phenyl ] sulfone (abbreviation: DMAC-DPS), 10-phenyl-10H, 10 ' H-spiro [ acridine-9, 9 ' -anthracene ] -10 ' -one (abbreviation: ACRSA), 4- (9 '-phenyl-3, 3' -bi-9H-carbazol-9-yl) benzofuro [3, 2-d ] pyrimidine (abbreviation: 4PCCzBfpm), 4- [4- (9 '-phenyl-3, 3' -bi-9H-carbazol-9-yl) phenyl ] benzofuro [3, 2-d ] pyrimidine (abbreviation: 4PCCzPBfpm), 9- [3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl ] -9 '-phenyl-2, 3' -bi-9H-carbazole (abbreviation: mPCCzPTzn-02), etc. having a pi-electron-rich heteroaromatic ring and a pi-electron-deficient heteroaromatic ring.
In addition, in the case where a pi-electron-rich heteroaromatic ring and a pi-electron-deficient heteroaromatic ring are directly bonded to each other, both donor and acceptor of the pi-electron-rich heteroaromatic ring are strong, and the energy difference between a singlet excited state and a triplet excited state is small, which is particularly preferable.
[ chemical formula 25]
Figure BDA0002659073460000971
In addition to the above, as the second organic compound 122 which is a material having a function of converting triplet excitation energy into light emission, a nanostructure of a transition metal compound having a perovskite structure can be given. Metal halide perovskite-based nanostructures are particularly preferable. As the nanostructure, nanoparticles and nanorods are preferable.
Examples of the light-emitting substance which converts a single excitation energy into light emission include substances which emit fluorescence (fluorescent light-emitting substances), and examples thereof include pyrene derivatives, anthracene derivatives, triphenylene derivatives, fluorene derivatives, carbazole derivatives, dibenzothiophene derivatives, dibenzofuran derivatives, dibenzoquinoxaline derivatives, pyridine derivatives, pyrimidine derivatives, phenanthrene derivatives, and naphthalene derivatives. In particular, the pyrene derivative is preferable because the luminescence quantum yield is high. Specific examples of the pyrene derivative include N, N ' -bis (3-methylphenyl) -N, N ' -bis [3- (9-phenyl-9H-fluoren-9-yl) phenyl ] pyrene-1, 6-diamine (abbreviated as 1, 6mMemFLPAPRn), N ' -diphenyl-N, N ' -bis [4- (9-phenyl-9H-fluoren-9-yl) phenyl ] pyrene-1, 6-diamine (abbreviated as 1, 6FLPAPRn), N ' -bis (dibenzofuran-2-yl) -N, N ' -diphenylpyrene-1, 6-diamine (abbreviated as 1, 6FrAPrn), N ' -bis (dibenzothiophene-2-yl) -N, n '-Diphenylpyrene-1, 6-diamine (abbreviated as 1, 6ThAPrn), N' - (pyrene-1, 6-diyl) bis [ (N-phenylbenzo [ b ] naphtho [1, 2-d ] furan) -6-amine ] (abbreviated as 1, 6BnfAPrn), N '- (pyrene-1, 6-diyl) bis [ (N-phenylbenzo [ b ] naphtho [1, 2-d ] furan) -8-amine ] (abbreviated as 1, 6BnfAPrn-02), N' - (pyrene-1, 6-diyl) bis [ (6, N-diphenylbenzo [ b ] naphtho [1, 2-d ] furan) -8-amine ] (abbreviated as 1, 6BnfAPrn-03), and the like.
In addition to the above, 5, 6-bis [4- (10-phenyl-9-anthracenyl) phenyl ] -2, 2 '-bipyridine (abbreviated as PAP2BPy), 5, 6-bis [ 4' - (10-phenyl-9-anthracenyl) biphenyl-4-yl ] -2, 2 '-bipyridine (abbreviated as PAPP2BPy), N' -bis [4- (9H-carbazol-9-yl) phenyl ] -N, N '-diphenylstilbene-4, 4' -diamine (abbreviated as YGA2S), 4- (9H-carbazol-9-yl) -4 '- (10-phenyl-9-anthracenyl) triphenylamine (abbreviated as YGAPA), 4- (9H-carbazol-9-yl) -4' - (9, 10-diphenyl-2-anthryl) triphenylamine (abbreviation: 2YGAPPA), N, 9-diphenyl-N- [4- (10-phenyl-9-anthracenyl) phenyl ] -9H-carbazol-3-amine (abbreviation: PCAPA), 4- (10-phenyl-9-anthracenyl) -4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviation: PCBAPA), 4- [4- (10-phenyl-9-anthracenyl) phenyl ] -4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviation: pcbappaba), perylene, 2, 5, 8, 11-tetra (tert-butyl) perylene (abbreviation: TBP), N ″ - (2-tert-butylanthracene-9, 10-diylbis-4, 1-phenylene) bis [ N, N' -triphenyl-1, 4-phenylenediamine ] (abbreviation: DPABPA), N, 9-diphenyl-N- [4- (9, 10-diphenyl-2-anthracenyl) phenyl ] -9H-carbazol-3-amine (abbreviation: 2PCAPPA), N- [4- (9, 10-diphenyl-2-anthryl) phenyl ] -N, N' -triphenyl-1, 4-phenylenediamine (abbreviation: 2DPAPPA), and the like.
Next, examples of the third organic compound 123 used as a host material of the light-emitting layer 113 include anthracene derivatives, tetracene derivatives, phenanthrene derivatives, pyrene derivatives, and perylene derivatives,
Figure BDA0002659073460000991
(chrysene) derivatives, dibenzo [ g, p ]]
Figure BDA0002659073460000992
Fused polycyclic aromatic compounds such as (chrysene) derivatives.
Specific examples of the above-mentioned compound include 9-phenyl-3- [4- (10-phenyl-9-anthryl) phenyl]-9H-carbazole (PCzPA), 3, 6-diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl]-9H-carbazole (abbreviated as DPCzPA), 3- [4- (1-naphthyl) -phenyl]-9-phenyl-9H-carbazole (PCPN), 9, 10-diphenylanthracene (DPAnth), N-diphenyl-9- [4- (10-phenyl-9-anthryl) phenyl]-9H-carbazole-3-amine (CzA 1PA for short), 4- (10-phenyl-9-anthryl) triphenylamine (DPhPA for short), YGAPA, PCAPA, N, 9-diphenyl-N- {4- [4- (10-phenyl-9-anthryl) phenyl group]Phenyl } -9H-carbazole-3-amine (PCAPBA), N- (9, 10-diphenyl-2-anthryl) -N, 9-diphenyl-9H-carbazole-3-amine (2 PCAPA), 6, 12-dimethoxy-5, 11-diphenyl
Figure BDA0002659073460000993
(chrysene), N, N, N ', N ', N ' -octaphenyldibenzo [ g, p ]]
Figure BDA0002659073460000994
(chrysene) -2, 7, 10, 15-tetramine (DBC 1 for short) and 9- [4- (10-phenyl-9-anthryl) phenyl ]-9H-carbazole (CzPA), 7- [4- (10-phenyl-9-anthryl) phenyl]-7H-dibenzo [ c, g]Carbazole (short for: cgDBCzPA), 6- [3- (9, 10-diphenyl-2-anthryl) phenyl]-benzo [ b ]]Naphtho [1, 2-d ]]Furan (abbreviation: 2mBnfPPA), 9-phenyl-10- {4- (9-phenyl-9H-fluoren-9-yl) biphenyl-4 '-yl } anthracene (abbreviation: FLPPA), 9, 10-bis (3, 5-diphenylphenyl) anthracene (abbreviation: DPPA), 9, 10-bis (2-naphthyl) anthracene (abbreviation: DNA), 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene (abbreviation: t-BuDNA), 9' -bianthracene (abbreviation: BANT), 9 '- (stilbene-3, 3' -diyl) phenanthrene (abbreviation: DPNS), 9 '- (stilbene-4, 4' -diyl) phenanthrene (abbreviation: DPNS2), 1, 3, 5-tris (1-pyrene) benzene (abbreviation: TPB3), 5, 12-diphenyltetracene, 5, 12-bis (biphenyl-2-yl) tetracene, and the like.
When the light-emitting substance is a phosphorescent light-emitting substance, examples of the organic compound (host material and auxiliary material) preferably used in combination with the phosphorescent light-emitting substance include aromatic amines, carbazole derivatives, dibenzothiophene derivatives, dibenzofuran derivatives, zinc-based metal complexes or aluminum-based metal complexes, oxadiazole derivatives, triazole derivatives, benzimidazole derivatives, quinoxaline derivatives, dibenzoquinoxaline derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, pyridine derivatives, bipyridine derivatives, and phenanthroline derivatives.
Specific examples thereof include 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1, 3, 4-oxadiazole (abbreviated as PBD), 1, 3-bis [5- (p-tert-butylphenyl) -1, 3, 4-oxadiazol-2-yl ] benzene (abbreviated as OXD-7), 9- [4- (5-phenyl-1, 3, 4-oxadiazol-2-yl) phenyl ] -9H-carbazole (abbreviated as CO11), 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1, 2, 4-triazole (abbreviated as TAZ), and 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenyl) 1, 2, 4-triazole (abbreviation: p-FtTAZ), and the like; 2, 2 '- (1, 3, 5-benzenetriyl) tris (1-phenyl-1H-benzimidazole) (abbreviated as TPBI), 2- [3- (dibenzothiophen-4-yl) phenyl ] -1-phenyl-1H-benzimidazole (abbreviated as mDBTBIm-II), 4' -bis (5-methylbenzoxazole-2-yl) stilbene (abbreviated as BzOs), bathophenanthroline (abbreviated as Bphen), bathocuproine (abbreviated as BCP), 2, 9-bis (naphthalen-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (abbreviated as NBphen), 2- [3- (dibenzothiophen-4-yl) phenyl ] dibenzo [ f, H ] quinoxaline (abbreviated as 2mDBTPDBq-II), 2- [3 '- (dibenzothiophen-4-yl) biphenyl-3-yl ] dibenzo [ f, H ] quinoxaline (abbreviated as 2mDBTBPDBq-II), 2- [ 3' - (9H-carbazol-9-yl) biphenyl-3-yl ] dibenzo [ f, H ] quinoxaline (abbreviated as 2mCZBPDBq), 2- [4- (3, 6-diphenyl-9H-carbazol-9-yl) phenyl ] dibenzo [ f, H ] quinoxaline (abbreviated as 2CZPDBq-III), 7- [3- (dibenzothiophen-4-yl) phenyl ] dibenzo [ f, H ] quinoxaline (abbreviated as 7mDBTPDBq-II) and 6- [3- (dibenzothiophen-4-yl) phenyl ] dibenzo [ f, h ] quinoxaline (abbreviated as 6mDBTPDBq-II) and other quinoxaline derivatives or dibenzoquinoxaline derivatives.
Examples thereof include pyrimidine derivatives such as 4, 6-bis [3- (phenanthrene-9-yl) phenyl ] pyrimidine (abbreviated as 4, 6mPnP2Pm), 4, 6-bis [3- (4-dibenzothienyl) phenyl ] pyrimidine (abbreviated as 4, 6mDBTP2Pm-II), 9' - (pyrimidine-4, 6-diylbis-3, 1-phenylene) bis (9H-carbazole) (abbreviated as 4, 6mCZP2 Pm); triazine derivatives such as 2- {4- [3- (N-phenyl-9H-carbazol-3-yl) -9H-carbazol-9-yl ] phenyl } -4, 6-diphenyl-1, 3, 5-triazine (abbreviation: PCCzPTzn), 9- [3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl ] -9 '-phenyl-2, 3' -bi-9H-carbazole (abbreviation: mPCzPTzn-02); pyridine derivatives such as 3, 5-bis [3- (9H-carbazol-9-yl) phenyl ] pyridine (abbreviated as 35DCzPPy) and 1, 3, 5-tris [3- (3-pyridine) phenyl ] benzene (abbreviated as TmPyPB); and the like.
In addition, polymer compounds such as poly (2, 5-pyridyldiyl) (abbreviated as PPy), poly [ (9, 9-dihexylfluorene-2, 7-diyl) -co- (pyridine-3, 5-diyl) ] (abbreviated as PF-Py), poly [ (9, 9-dioctylfluorene-2, 7-diyl) -co- (2, 2 '-bipyridine-6, 6' -diyl) ] (abbreviated as PF-BPy) and the like can be used.
< Electron transport layer >
The electron transport layer 114 is a layer that transports electrons injected from the second electrode 102 through an electron injection layer 115 described later to the light-emitting layer 113. Further, the electron transporting layer 114 is a layer containing an electron transporting material. The electron-transporting material used for the electron-transporting layer 114 preferably has a thickness of 1 × 10 -6cm2A substance having an electron mobility of greater than/Vs. In addition, any substance other than the above may be used as long as it has a higher electron-transport property than a hole-transport property. The electron transport layers (114, 114a, 114b) function as a single layer, but when a stacked structure of two or more layers is used as necessary, device characteristics can be improved.
As the organic compound that can be used for the electron transport layer 114, an organic compound having a structure in which a furan ring having a furodiazine skeleton is fused with an aromatic ring, a metal complex having a quinoline skeleton, a metal complex having a benzoquinoline skeleton, a metal complex having an oxazole skeleton, a metal complex having a thiazole skeleton, or the like can be used, and a material having high electron transport properties (electron transport material) such as an oxadiazole derivative, a triazole derivative, an imidazole derivative, an oxazole derivative, a thiazole derivative, a phenanthroline derivative, a quinoline derivative having a quinoline ligand, a benzoquinoline derivative, a quinoxaline derivative, a dibenzoquinoxaline derivative, a pyridine derivative, a bipyridine derivative, a pyrimidine derivative, a nitrogen-containing heteroaromatic compound having a pi-electron deficiency type, or the like can also be used.
Specific examples of the electron-transporting material include: 2- [ 3' - (dibenzothiophen-4-yl) biphenyl-3-yl]Dibenzo [ f, h ]]Quinoxaline (abbreviation: 2mDBTBPDBq-II), 2- [ 3' - (dibenzothiophen-4-yl) biphenyl-3-yl]Dibenzo [ f, h ]]Quinoxaline (abbreviation: 2mDBTBPDBq-II), 5- [3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl]-7, 7-dimethyl-5H, 7H-indeno [2, 1-b ]]Carbazole (abbreviated as mINC (II) PTzn), 4- [3- (dibenzothiophen-4-yl) phenyl]-8- (naphthalen-2-yl) - [1]Benzofuro [3, 2-d]Pyrimidine (short for: 8 beta N-4mDBtPBfpm), 3, 8-bis [3- (dibenzothiophene-4-yl) phenyl]Benzofuro [2, 3-b ]]Pyrazine (abbreviation: 3, 8mDBtP2Bfpr), 4, 8-bis [3- (dibenzothiophene)-4-yl) phenyl]-[1]Benzofuro [3, 2-d]Pyrimidine (short for: 4, 8mDBtP2Bfpm), 9- [ (3' -dibenzothiophene-4-yl) biphenyl-3-yl]Naphtho [1 ', 2': 4,5]Furo [2, 3-b ] s]Pyrazine (abbreviation: 9 mDBtPNfpr), 8- [3 '- (dibenzothiophene-4-yl) (1, 1' -biphenyl-3-yl)]Naphtho [1 ', 2': 4,5]Furo [3, 2-d ] s]Pyrimidine (abbreviation: 8 mDBtPNfpm), 8- [ (2, 2' -binaphthyl) -6-yl]-4- [3- (dibenzothiophen-4-yl) phenyl- [1]Benzofuro [3, 2-d ]Pyrimidine (short for 8 (beta N2) -4mDBtPBfpm) and tris (8-hydroxyquinoline) aluminum (III) (short for Alq)3) Tris (4-methyl-8-quinolinolato) aluminum (III) (abbreviation: almq3) Bis (10-hydroxybenzo [ h ]]Quinoline) beryllium (II) (abbreviation: BeBq2) Bis (2-methyl-8-quinolinol) (4-phenylphenol) aluminum (III) (abbreviation: BAlq), bis (8-hydroxyquinoline) zinc (II) (abbreviation: znq) and the like having a quinoline skeleton or a benzoquinoline skeleton; bis [2- (2-benzoxazolyl) phenol]Zinc (II) (ZnPBO for short), bis [2- (2-benzothiazolyl) phenol]Zinc (II) (ZnBTZ for short), bis [2- (2-hydroxyphenyl) benzothiazole]Zinc (II) (abbreviated as Zn (BTZ))2) And metal complexes having an oxazole skeleton or a thiazole skeleton.
In addition to the metal complex, oxadiazole derivatives such as PBD, OXD-7 and CO 11; triazole derivatives such as TAZ and p-EtTAZ; imidazole derivatives (including benzimidazole derivatives) such as TPBI, mDBTBIm-II, etc.; oxazole derivatives such as BzOs; phenanthroline derivatives such as Bphen, BCP, NBphen, etc.; quinoxaline derivatives or dibenzoquinoxaline derivatives such as 2mDBTPDBq-II, 2 mDBTPBq-II, 2mCZBPDBq, 2CZPDBq-III, 7mDBTPDBq-II, 6mDBTPDBq-II, etc.; pyridine derivatives such as 35DCzPPy and TmPyPB; pyrimidine derivatives such as 4, 6mPnP2Pm, 4, 6mDBTP2Pm-II, 4, 6mCzP2Pm, and the like; triazine derivatives such as PCCzPTzn and mPCzPTzn-02.
Furthermore, polymer compounds such as PPy, PF-Py and PF-BPy can also be used.
< Electron injection layer >
The electron injection layer 115 is a layer for improving the efficiency of electron injection from the second electrode (cathode) 102, and it is preferable to use a value of the work function of the material for the second electrode (cathode) 102 and a material for the electron injection layer 115A material having a small difference in LUMO level value (0.5eV or less). Therefore, as the electron injection layer 115, lithium, cesium, lithium fluoride (LiF), cesium fluoride (CsF), and calcium fluoride (CaF) can be used2) And 8- (hydroxyquinoxaline) lithium (abbreviation: liq), lithium 2- (2-pyridyl) phenoxide (abbreviation: LiPP), 2- (2-pyridyl) -3-hydroxypyridine (pyridinolato) lithium (abbreviation: LiPPy), lithium 4-phenyl-2- (2-pyridyl) phenoxide (abbreviation: LiPPP), lithium oxide (LiO)x) And alkali metals, alkaline earth metals, or compounds thereof such as cesium carbonate. In addition, erbium fluoride (ErF) may be used3) And the like.
Further, as in the light-emitting device shown in fig. 6B, by providing the charge generation layer 104 between the two EL layers (103a and 103B), a structure in which a plurality of EL layers are stacked between a pair of electrodes (also referred to as a series structure) can be provided. Note that in this embodiment mode, the functions and materials of the hole injection layer (111), the hole transport layer (112), the light-emitting layer (113), the electron transport layer (114), and the electron injection layer (115) described in fig. 6A are the same as those of the hole injection layer (111a, 111B), the hole transport layer (112a, 112B), the light-emitting layer (113a, 113B), the electron transport layer (114a, 114B), and the electron injection layer (115a, 115B) described in fig. 6B.
< Charge generation layer >
In the light-emitting device shown in fig. 6B, the charge generation layer 104 has the following functions: when a voltage is applied between the first electrode 101 (anode) and the second electrode 102 (cathode), electrons are injected into the EL layer 103a and holes are injected into the EL layer 103 b. The charge generation layer 104 may have a structure in which an electron acceptor (acceptor) is added to a hole-transporting material, or may have a structure in which an electron donor (donor) is added to an electron-transporting material. Alternatively, these two structures may be stacked. Further, by forming the charge generation layer 104 using the above-described material, an increase in driving voltage at the time of stacking the EL layers can be suppressed.
When the charge generation layer 104 has a structure in which an electron acceptor is added to a hole-transporting material, the materials described in this embodiment mode can be used as the hole-transporting material. Further, examples of the electron acceptor include 7, 7, 8, 8-tetracyano-2,3, 5, 6-tetrafluoroquinodimethane (abbreviation: F)4-TCNQ), chloranil, and the like. Further, oxides of metals belonging to groups 4 to 8 of the periodic table may be mentioned. Specific examples thereof include vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and rhenium oxide.
In the case where the charge generation layer 104 has a structure in which an electron donor is added to an electron transporting material, the materials described in this embodiment mode can be used as the electron transporting material. Further, as the electron donor, an alkali metal, an alkaline earth metal, a rare earth metal, or a metal belonging to group 2 or group 13 of the periodic table of the elements, and an oxide or a carbonate thereof can be used. Specifically, lithium (Li), cesium (Cs), magnesium (Mg), calcium (Ca), ytterbium (Yb), indium (In), lithium oxide, cesium carbonate, and the like are preferably used. Further, an organic compound such as tetrathianaphtalene (tetrathianaphtalene) may also be used as the electron donor.
Although fig. 6B shows a structure in which two EL layers (103a and 103B) are stacked, it is possible to make a stacked structure of three or more by providing a charge generation layer between different EL layers.
< substrate >
The light-emitting device shown in this embodiment mode can be formed over various substrates. Note that there is no particular limitation on the kind of the substrate. Examples of the substrate include a semiconductor substrate (e.g., a single crystal substrate or a silicon substrate), an SOI substrate, a glass substrate, a quartz substrate, a plastic substrate, a metal substrate, a stainless steel substrate, a substrate including a stainless steel foil, a tungsten substrate, a substrate including a tungsten foil, a flexible substrate, a bonding film, a paper film including a fibrous material, a base film, and the like.
Examples of the glass substrate include barium borosilicate glass, aluminoborosilicate glass, and soda lime glass. Examples of the flexible substrate, the adhesive film, and the base film include plastics typified by polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyether sulfone (PES), synthetic resins such as acrylic resins, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyamide, polyimide, aramid resins, epoxy resins, inorganic vapor-deposited films, and paper.
In addition, when the light-emitting device described in this embodiment mode is manufactured, a vacuum process such as a vapor deposition method or a solution process such as a spin coating method or an ink jet method can be used. As the vapor deposition method, a physical vapor deposition method (PVD method) such as a sputtering method, an ion plating method, an ion beam vapor deposition method, a molecular beam vapor deposition method, or a vacuum vapor deposition method, a chemical vapor deposition method (CVD method), or the like can be used. In particular, the functional layer (the hole injection layer (111, 111a, 111b), the hole transport layer (112, 112a, 112b), the light emitting layer (113, 113a, 113b), the electron transport layer (114, 114a, 114b), the electron injection layer (115, 115a, 115b)) and the charge generation layer (104) included in the EL layer of the light emitting device can be formed by a method such as a vapor deposition method (vacuum vapor deposition method), a coating method (dip coating method, dye coating method, bar coating method, spin coating method, spray coating method, or the like), a printing method (an ink jet method, screen printing (stencil printing) method, offset printing (lithography) method, flexography (relief printing) method, gravure printing method, microcontact printing method, nanoimprint method, or the like).
The materials of the functional layers (the hole injection layers (111, 111a, 111b), the hole transport layers (112, 112a, 112b), the light emitting layers (113, 113a, 113b), the electron transport layers (114, 114a, 114b), the electron injection layers (115, 115a, 115b)) and the charge generation layer (104)) constituting the EL layers (103, 103a, 103b) of the light emitting device shown in this embodiment mode are not limited to these materials, and any material may be used in combination as long as the material can satisfy the functions of each layer. As an example, a high molecular compound (oligomer, dendrimer, polymer, etc.), a medium molecular compound (compound between low and high molecules: molecular weight 400 to 4000), an inorganic compound (quantum dot material, etc.), or the like can be used. As the quantum dot material, a colloidal quantum dot material, an alloy type quantum dot material, a Core Shell (Core Shell) type quantum dot material, a Core type quantum dot material, or the like can be used.
The structure described in this embodiment can be used in combination with the structures described in the other embodiments as appropriate.
Embodiment 4
In this embodiment, a light-emitting device according to one embodiment of the present invention will be described. The light-emitting device shown in fig. 7A is an active matrix light-emitting device in which a transistor (FET)202 and light-emitting devices (203R, 203G, 203B, and 203W) formed over a first substrate 201 are electrically connected, and a microcavity structure in which an EL layer 204 is used in common for a plurality of light-emitting devices (203R, 203G, 203B, and 203W) and an optical distance between electrodes of each light-emitting device is adjusted so that a desired emission color of each light-emitting device is obtained is employed. Further, a top emission type light-emitting device is employed in which light obtained from the EL layer 204 is emitted through color filters (206R, 206G, 206B) formed on the second substrate 205.
In the light-emitting device shown in fig. 7A, the first electrode 207 is used as a reflective electrode, and the second electrode 208 is used as a transflective electrode having both transparency and reflectivity to light (visible light or near-infrared light). As an electrode material for forming the first electrode 207 and the second electrode 208, any electrode material can be used as appropriate with reference to other embodiments.
Further, in fig. 7A, for example, in the case where the light emitting devices 203R, 203G, 203B, 203W are respectively a red light emitting device, a green light emitting device, a blue light emitting device, a white light emitting device, as shown in fig. 7B, the distance between the first electrode 207 and the second electrode 208 in the light emitting device 203R is adjusted to the optical distance 200R, the distance between the first electrode 207 and the second electrode 208 in the light emitting device 203G is adjusted to the optical distance 200G, and the distance between the first electrode 207 and the second electrode 208 in the light emitting device 203B is adjusted to the optical distance 200B. Further, as shown in fig. 7B, optical adjustment can be performed by laminating the conductive layer 210R on the first electrode 207 in the light emitting device 203R and the conductive layer 210G on the first electrode 207 in the light emitting device 203G.
Color filters (206R, 206G, 206B) are formed on the second substrate 205. The color filter transmits visible light in a specific wavelength range and blocks visible light in the specific wavelength range. Therefore, as shown in fig. 7A, by providing a color filter 206R that transmits only light in the red wavelength range at a position overlapping with the light-emitting device 203R, red light can be obtained from the light-emitting device 203R. Further, by providing the color filter 206G which transmits only light in the green wavelength range at a position overlapping with the light emitting device 203G, green light can be obtained from the light emitting device 203G. Further, by providing the color filter 206B which transmits only light in the blue wavelength range at a position overlapping with the light-emitting device 203B, blue light can be obtained from the light-emitting device 203B. However, white light can be obtained from the light emitting device 203W without providing a filter. Further, a black layer (black matrix) 209 may be provided at an end portion of each color filter. The color filters (206R, 206G, 206B) or the black layer 209 may be covered with a protective layer made of a transparent material.
Although the light-emitting device of the structure (top emission type) in which light is extracted on the second substrate 205 side is shown in fig. 7A, a light-emitting device of the structure (bottom emission type) in which light is extracted on the first substrate 201 side where the FET202 is formed as shown in fig. 7C may be employed. In the bottom emission type light emitting device, the first electrode 207 is used as a semi-transmissive-semi-reflective electrode, and the second electrode 208 is used as a reflective electrode. As the first substrate 201, at least a substrate having a light-transmitting property is used. As shown in fig. 7C, the color filters (206R ', 206G ', 206B ') may be provided on the side closer to the first substrate 201 than the light-emitting devices (203R, 203G, 203B).
In fig. 7A, a case where the light-emitting device is a red light-emitting device, a green light-emitting device, a blue light-emitting device, or a white light-emitting device is shown, but the light-emitting device according to one embodiment of the present invention is not limited to this structure, and a yellow light-emitting device or an orange light-emitting device may be used. As a material for manufacturing an EL layer (a light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, a charge generation layer, or the like) of these light-emitting devices, it can be used as appropriate with reference to other embodiments. In this case, it is necessary to appropriately select the color filter according to the emission color of the light emitting device.
By adopting the above configuration, a light-emitting device including a light-emitting device that emits light of a plurality of colors can be obtained.
The structure described in this embodiment can be used in combination with the structures described in the other embodiments as appropriate.
Embodiment 5
In this embodiment, a light-emitting device which is one embodiment of the present invention will be described.
By using the device structure of the light-emitting device according to one embodiment of the present invention, an active matrix light-emitting device or a passive matrix light-emitting device can be manufactured. In addition, the active matrix light-emitting device has a structure in which a light-emitting device and a transistor (FET) are combined. Thus, both the passive matrix light-emitting device and the active matrix light-emitting device are included in one embodiment of the present invention. Further, the light-emitting device shown in other embodiments can be applied to the light-emitting apparatus shown in this embodiment.
In this embodiment, an active matrix light-emitting device will be described with reference to fig. 8A and 8B.
Fig. 8A is a plan view of the light emitting device, and fig. 8B is a sectional view cut along a chain line a-a' in fig. 8A. An active matrix light-emitting device includes a pixel portion 302, a driver circuit portion (source line driver circuit) 303, and a driver circuit portion (gate line driver circuit) (304a and 304b) provided over a first substrate 301. The pixel portion 302 and the driver circuit portions (303, 304a, 304b) are sealed between the first substrate 301 and the second substrate 306 with a sealant 305.
A lead 307 is provided over the first substrate 301. The lead wire 307 is electrically connected to an FPC308 as an external input terminal. The FPC308 is used to transmit signals (for example, video signals, clock signals, start signals, reset signals, or the like) or potentials from the outside to the driver circuit portions (303, 304a, 304 b). In addition, the FPC308 may be mounted with a Printed Wiring Board (PWB). The state in which such FPC or PWB is mounted may be included in the category of the light-emitting device.
Fig. 8B shows a sectional structure.
The pixel portion 302 is configured by a plurality of pixels each having an FET (switching FET)311, an FET (current control FET)312, and a first electrode 313 electrically connected to the FET 312. The number of FETs provided in each pixel is not particularly limited, and may be appropriately set as necessary.
The FETs 309, 310, 311, and 312 are not particularly limited, and for example, staggered transistors or inversely staggered transistors may be used. Further, a transistor structure of a top gate type, a bottom gate type, or the like may be employed.
Further, the crystallinity of a semiconductor which can be used for the FETs 309, 310, 311, and 312 is not particularly limited, and any of an amorphous semiconductor and a semiconductor having crystallinity (a microcrystalline semiconductor, a polycrystalline semiconductor, a single crystal semiconductor, or a semiconductor a part of which has a crystalline region) can be used. The use of a semiconductor having crystallinity is preferable because deterioration of transistor characteristics can be suppressed.
As the semiconductor, for example, a group 14 element, a compound semiconductor, an oxide semiconductor, an organic semiconductor, or the like can be used. Typically, a semiconductor containing silicon, a semiconductor containing gallium arsenide, an oxide semiconductor containing indium, or the like can be used.
The driver circuit portion 303 includes FETs 309 and 310. The driver circuit portion 303 may be formed of a circuit including a transistor having a single polarity (either of N-type and P-type), or may be formed of a CMOS circuit including an N-type transistor and a P-type transistor. Further, a configuration having a driving circuit outside may be employed.
The end of the first electrode 313 is covered with an insulator 314. As the insulator 314, an organic compound such as a negative photosensitive resin or a positive photosensitive resin (acrylic resin) or an inorganic compound such as silicon oxide, silicon oxynitride, or silicon nitride can be used. The upper or lower end of the insulator 314 preferably has a curved surface with curvature. This makes it possible to provide a film formed on the insulator 314 with good coverage.
An EL layer 315 and a second electrode 316 are stacked over the first electrode 313. The EL layer 315 includes a light-emitting layer, a hole-injecting layer, a hole-transporting layer, an electron-injecting layer, a charge-generating layer, and the like.
As the structure of the light-emitting device 317 described in this embodiment mode, structures or materials described in other embodiment modes can be applied. Although not shown here, the second electrode 316 is electrically connected to the FPC308 serving as an external input terminal.
Although only one light emitting device 317 is illustrated in the cross-sectional view illustrated in fig. 8B, a plurality of light emitting devices are arranged in a matrix in the pixel portion 302. By selectively forming light-emitting devices capable of emitting light of three (R, G, B) colors in the pixel portion 302, a light-emitting device capable of full-color display can be formed. In addition to the light-emitting device capable of obtaining light emission of three (R, G, B) colors, for example, a light-emitting device capable of obtaining light emission of colors such as white (W), yellow (Y), magenta (M), and cyan (C) may be formed. For example, by adding a light-emitting device capable of obtaining the above-described plurality of types of light emission to a light-emitting device capable of obtaining light emission of three (R, G, B) colors, effects such as improvement in color purity and reduction in power consumption can be obtained. Further, a light-emitting device capable of full-color display may be realized by combining with a color filter. As the type of the color filter, red (R), green (G), blue B, cyan C, magenta (M), yellow (Y), and the like can be used.
By attaching the second substrate 306 to the first substrate 301 using the sealant 305, the FETs (309, 310, 311, 312) and the light emitting device 317 over the first substrate 301 are located in a space 318 surrounded by the first substrate 301, the second substrate 306, and the sealant 305. In addition, the space 318 may be filled with an inert gas (e.g., nitrogen, argon, or the like) or may be filled with an organic substance (including the sealant 305).
Epoxy or glass frit may be used as the sealant 305. As the sealing agent 305, a material which does not transmit moisture or oxygen as much as possible is preferably used. In addition, the same material as that of the first substrate 301 can be used for the second substrate 306. Thus, various substrates shown in other embodiments can be used. As the substrate, a plastic substrate made of FRP (Fiber-Reinforced Plastics), PVF (polyvinyl fluoride), polyester, acrylic resin, or the like can be used in addition to a glass substrate and a quartz substrate. In the case where glass frit is used as a sealant, a glass substrate is preferably used for the first substrate 301 and the second substrate 306 in view of adhesiveness.
As described above, an active matrix light-emitting device can be obtained.
In the case of forming an active matrix light-emitting device over a flexible substrate, the FET and the light-emitting device may be formed directly over the flexible substrate, or the FET and the light-emitting device may be formed over another substrate having a release layer, and then the FET and the light-emitting device may be separated from each other by applying heat, force, laser irradiation, or the like to the release layer and then transferred to the flexible substrate. The release layer may be, for example, a laminate of an inorganic film such as a tungsten film and a silicon oxide film, or an organic resin film such as polyimide. In addition to a substrate in which a transistor can be formed, examples of the flexible substrate include a paper substrate, a cellophane substrate, an aramid film substrate, a polyimide film substrate, a cloth substrate (including natural fibers (silk, cotton, hemp), synthetic fibers (nylon, polyurethane, polyester), regenerated fibers (acetate fibers, cuprammonium fibers, rayon, regenerated polyester), and the like), a leather substrate, a rubber substrate, and the like. By using such a substrate, it is possible to realize excellent resistance and heat resistance, and to reduce the weight and thickness of the substrate.
In driving a light-emitting device included in an active matrix light-emitting device, the light-emitting device can emit light in a pulse form (for example, using a frequency such as kHz or MHz) and use the light for display. The light emitting device formed using the above organic compound has excellent frequency characteristics, and can reduce the driving time of the light emitting device to reduce power consumption. Further, heat generation due to the shortening of the driving time is suppressed, whereby deterioration of the light emitting device can be reduced.
The structure described in this embodiment can be used in combination with the structures described in the other embodiments as appropriate.
Embodiment 6
In this embodiment, examples of various electronic devices and automobiles each using the light-emitting device according to one embodiment of the present invention or the light-emitting device including the light-emitting device according to one embodiment of the present invention will be described. Note that the light-emitting device can be mainly used for the display portion in the electronic apparatus described in this embodiment mode.
The electronic apparatus shown in fig. 9A to 9E may include a housing 7000, a display portion 7001, a speaker 7003, an LED lamp 7004, operation keys 7005 (including a power switch or an operation switch), connection terminals 7006, a sensor 7007 (having a function of measuring a force, a displacement, a position, a velocity, an acceleration, an angular velocity, a rotational speed, a distance, light, liquid, magnetism, a temperature, a chemical substance, sound, time, hardness, an electric field, current, voltage, electric power, radiation, a flow rate, humidity, inclination, vibration, odor, or infrared ray), a microphone 7008, and the like.
Fig. 9A shows a mobile computer which can include a switch 7009, an infrared port 7010, and the like in addition to the above.
Fig. 9B shows a portable image reproducing apparatus (for example, a DVD reproducing apparatus) provided with a recording medium, which can include the second display portion 7002, the recording medium reading portion 7011, and the like in addition to the above.
Fig. 9C shows a digital camera having a television receiving function, which can include an antenna 7014, a shutter button 7015, an image receiving portion 7016, and the like in addition to the above.
Fig. 9D shows a portable information terminal. The portable information terminal has a function of displaying information on three or more surfaces of the display portion 7001. Here, an example is shown in which the information 7052, the information 7053, and the information 7054 are displayed on different surfaces. For example, in a state where the portable information terminal is placed in a jacket pocket, the user can confirm the information 7053 displayed at a position viewed from above the portable information terminal. The user can confirm the display without taking out the portable information terminal from the pocket and can judge whether to answer the call.
Fig. 9E shows a portable information terminal (including a smartphone), which can include a display portion 7001, operation keys 7005, and the like in a housing 7000. The portable information terminal may be provided with a speaker 7003, a connection terminal 7006, a sensor 7007, and the like. Further, the portable information terminal can display text or image information on a plurality of faces thereof. Here, an example in which three icons 7050 are displayed is shown. Further, information 7051 indicated by a dotted rectangle may be displayed on the other surface of the display portion 7001. Examples of the information 7051 include information for prompting reception of an email, SNS (Social Networking Services), a telephone, or the like; titles of e-mails or SNS, etc.; a sender name of an email, SNS, or the like; a date; time; the remaining amount of the battery; and antenna received signal strength, etc. Alternatively, an icon 7050 or the like may be displayed at a position where the information 7051 is displayed.
Fig. 9F shows a large-sized television device (also referred to as a television or a television receiver), which may include a housing 7000, a display portion 7001, and the like. Further, the structure of the housing 7000 supported by the stand 7018 is shown here. Further, the television apparatus can be operated by using a remote controller 7111 or the like which is separately provided. The display portion 7001 may be provided with a touch sensor, and the display portion 7001 may be touched with a finger or the like to be operated. The remote controller 7111 may include a display unit for displaying data output from the remote controller 7111. By using an operation key or a touch panel provided in the remote controller 7111, a channel and a volume can be operated, and an image displayed on the display portion 7001 can be operated.
The electronic devices shown in fig. 9A to 9F may have various functions. For example, the following functions may be provided: a function of displaying various information (still image, moving image, character image, and the like) on the display unit; a touch panel function; a function of displaying a calendar, date, time, or the like; a function of controlling processing by using various software (programs); a wireless communication function; a function of connecting to various computer networks by using a wireless communication function; a function of transmitting or receiving various data by using a wireless communication function; a function of reading out a program or data stored in a recording medium and displaying the program or data on a display unit. Further, an electronic apparatus including a plurality of display portions may have a function of mainly displaying image information on one display portion and mainly displaying text information on another display portion, a function of displaying a three-dimensional image by displaying an image in consideration of parallax on a plurality of display portions, or the like. Further, the electronic device having the image receiving unit may have the following functions: a function of shooting a still image; a function of shooting a moving image; a function of automatically or manually correcting the captured image; a function of storing a captured image in a recording medium (external or built-in camera); a function of displaying the captured image on a display unit, and the like. Note that the functions that the electronic apparatuses shown in fig. 9A to 9F may have are not limited to the above-described functions, but may have various functions.
Fig. 9G is a wristwatch-type portable information terminal that can be used as a timepiece-type electronic device, for example. The wristwatch-type portable information terminal includes a housing 7000, a display portion 7001, operation buttons 7022, 7023, a connection terminal 7024, a band 7025, a microphone 7026, a sensor 7029, a speaker 7030, and the like. Since the display surface of the display portion 7001 is curved, display can be performed along the curved display surface. Further, the wristwatch-type portable information terminal can perform a handsfree call by communicating with a headset that can perform wireless communication, for example. In addition, data transmission or charging with another information terminal can be performed by using the connection terminal 7024. Charging may also be by wireless power.
The display portion 7001 mounted in the housing 7000 also serving as a frame (bezel) portion has a display region having a non-rectangular shape. The display unit 7001 can display an icon indicating time, other icons, and the like. The display portion 7001 may be a touch panel (input/output device) to which a touch sensor (input device) is attached.
The timepiece-type electronic device shown in fig. 9G may have various functions. For example, the following functions may be provided: a function of displaying various information (still image, moving image, character image, and the like) on the display unit; a touch panel function; a function of displaying a calendar, date, time, or the like; a function of controlling processing by using various software (programs); a wireless communication function; a function of connecting to various computer networks by using a wireless communication function; a function of transmitting or receiving various data by using a wireless communication function; a function of reading out a program or data stored in a recording medium and displaying the program or data on a display unit.
The interior of the housing 7000 may be provided with a speaker, a sensor (having a function of measuring a force, a displacement, a position, a velocity, an acceleration, an angular velocity, a rotational speed, a distance, light, liquid, magnetism, temperature, a chemical substance, sound, time, hardness, an electric field, current, voltage, electric power, radiation, flow, humidity, inclination, vibration, smell, or infrared ray), a microphone, or the like.
The light-emitting device according to one embodiment of the present invention can be used for each display portion of the electronic device described in this embodiment, whereby a long-life electronic device can be realized.
As an electronic device using a light-emitting device, a foldable portable information terminal shown in fig. 10A to 10C can be given. Fig. 10A shows the portable information terminal 9310 in an expanded state. Fig. 10B shows the portable information terminal 9310 in a state halfway through the transition from one state to the other state of the expanded state and the folded state. Fig. 10C shows a portable information terminal 9310 in a folded state. The portable information terminal 9310 has good portability in the folded state and has a large display area seamlessly connected in the unfolded state, so that it has a high display list.
The display portion 9311 is supported by three housings 9315 connected by hinge portions 9313. The display portion 9311 may be a touch panel (input/output device) to which a touch sensor (input device) is attached. Further, the display portion 9311 can be reversibly changed from the folded state to the unfolded state of the portable information terminal 9310 by folding the two housings 9315 with the hinge portions 9313. A light-emitting device according to one embodiment of the present invention can be used for the display portion 9311. Further, a long-life electronic apparatus can be realized. The display region 9312 in the display portion 9311 is a display region located on the side of the portable information terminal 9310 in a folded state. An information icon, a shortcut of an application or program that is frequently used, or the like can be displayed in the display region 9312, and information can be confirmed or the application can be started smoothly.
Fig. 11A and 11B show an automobile using a light-emitting device. That is, the light emitting device may be formed integrally with the automobile. Specifically, the present invention can be applied to a lamp 5101 (including a rear body portion) on the outer side of the automobile shown in fig. 11A, a hub 5102 of a tire, a part or the whole of a door 5103, and the like. The present invention can be applied to a display portion 5104, a steering wheel 5105, a shift lever 5106, a seat 5107, an interior mirror 5108, a windshield 5109, and the like on the inside of the automobile shown in fig. 11B. In addition to this, it can also be used for a part of a glazing.
As described above, an electronic device or an automobile using the light-emitting device of one embodiment of the present invention can be obtained. In this case, a long-life electronic apparatus can be realized. The electronic device or the automobile that can be used is not limited to the electronic device or the automobile described in this embodiment, and can be applied to various fields.
Note that the structure described in this embodiment can be used in appropriate combination with the structures described in other embodiments.
Embodiment 7
In this embodiment, a structure of an illumination device manufactured by applying a light-emitting device according to one embodiment of the present invention or a part of a light-emitting device thereof will be described with reference to fig. 12 and 13.
Fig. 12 and 13 show examples of cross-sectional views of the lighting device. Fig. 12 is a bottom emission type lighting device extracting light on the substrate side, and fig. 13 is a top emission type lighting device extracting light on the sealing substrate side.
The lighting apparatus 4000 illustrated in fig. 12 includes a light-emitting device 4002 over a substrate 4001. Further, the lighting device 4000 includes a substrate 4003 having irregularities on the outer side of the substrate 4001. The light-emitting device 4002 includes a first electrode 4004, an EL layer 4005, and a second electrode 4006.
The first electrode 4004 is electrically connected to the electrode 4007, and the second electrode 4006 is electrically connected to the electrode 4008. Further, an auxiliary wiring 4009 electrically connected to the first electrode 4004 may be provided. Further, an insulating layer 4010 is formed over the auxiliary wiring 4009.
The substrate 4001 and the sealing substrate 4011 are bonded by a sealant 4012. Further, a drying agent 4013 is preferably provided between the sealing substrate 4011 and the light-emitting device 4002. Since the substrate 4003 has irregularities as shown in fig. 12, the extraction efficiency of light generated in the light-emitting device 4002 can be improved.
The lighting device 4200 shown in fig. 13 includes a light emitting device 4202 on a substrate 4201. The light emitting device 4202 includes a first electrode 4204, an EL layer 4205, and a second electrode 4206.
The first electrode 4204 is electrically connected to the electrode 4207, and the second electrode 4206 is electrically connected to the electrode 4208. In addition, an auxiliary wiring 4209 electrically connected to the second electrode 4206 may be provided. Further, an insulating layer 4210 may be provided under the auxiliary wiring 4209.
The substrate 4201 and the sealing substrate 4211 having the concave and convex are bonded by a sealant 4212. Further, a barrier film 4213 and a planarization film 4214 may be provided between the sealing substrate 4211 and the light-emitting device 4202. Since the sealing substrate 4211 has irregularities as shown in fig. 13, the extraction efficiency of light generated in the light-emitting device 4202 can be improved.
An example of an application of the lighting device is a ceiling lamp for indoor lighting. As the ceiling spotlight, there are a ceiling-mounted type lamp, a ceiling-embedded type lamp, and the like. Such lighting means may be constituted by a combination of light emitting means and a housing or cover.
In addition, the present invention can be applied to a footlight that can illuminate the ground to improve safety. For example, the footlight can be effectively used in bedrooms, stairs, passageways, and the like. In this case, the size or shape of the room may be appropriately changed according to the size or structure thereof. Further, the light emitting device and the support base may be combined to constitute a mounting type lighting device.
Further, the present invention can also be applied to a film-like lighting device (sheet lighting). Since the sheet lighting is used by being attached to a wall, it can be applied to various uses in a space-saving manner. In addition, a large area can be easily realized. In addition, it can also be attached to a wall or housing having a curved surface.
By using the light-emitting device according to one embodiment of the present invention or a part of the light-emitting device thereof in a part of indoor furniture other than the above, a lighting device having a function of furniture can be provided.
As described above, various lighting devices using the light-emitting device can be obtained. Further, such a lighting device is included in one embodiment of the present invention.
The structure described in this embodiment can be implemented in appropriate combination with the structures described in the other embodiments.
Example 1
Synthesis example 1
In this example, a method for synthesizing a compound of one embodiment of the present invention represented by the structural formula (100) of embodiment 1, that is, N '-bis [3, 5-bis (2-adamantyl) phenyl ] -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviated as 2 Ph-mmadtudpha 2 anthh) will be described. The structure of 2Ph-mmAdtBuDPhA2Anth is shown below.
[ chemical formula 30]
Figure BDA0002659073460001201
< step 1: synthesis of 3- (2-adamantyl) -5-bromoanisole
5.3g (20mmol) of 3, 5-dibromoanisole was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 200mL of tetrahydrofuran, and the mixture was stirred at-80 ℃. To the solution, 14mL (22mmol) of n-butyllithium (1.6mol/L n-hexane solution) was added dropwise, and the mixture was stirred under a nitrogen stream for 2 hours. Then, 3.7g (25mmol) of 2-adamantanone was added to the mixture, and the mixture was stirred for 15 hours while gradually raising the temperature back to room temperature.
After stirring, water was added to the mixture, and the aqueous layer was extracted with ethyl acetate. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
The obtained oily substance was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 200mL of methylene chloride, and the mixture was stirred at 0 ℃. To the solution was added 9.6mL (60mmol) of triethylsilane and 15mL (120mmol) of boron trifluoride diethyl ether dropwise, and the mixture was stirred for 15 hours while the temperature was raised to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
This oil was purified by silica gel column chromatography (hexane: toluene: 4: 1 as developing solvent) to obtain the desired product as a white solid. The obtained solid was purified by HPLC (developing solvent: chloroform), whereby 3.1g of the objective white solid was obtained in a yield of 48%. The synthesis scheme (a-1) of step 1 is shown below.
[ chemical formula 31]
Figure BDA0002659073460001211
Further, the following shows the utilization of the white solid obtained in the above step 11Measurement result of H NMR. From the results, 3- (2-adamantyl) -5-bromoanisole was obtained.
1HNMR(CDCl3，300MHz)：σ＝7.09-7.08(m、1H)、6.88-6.82(m、2H)、3.79(s、3H)、2.93(m、1H)、2.39(m、2H)、2.01-1.77(m、11H)、1.58(m、1H)。
< step 2: synthesis of 3, 5-bis (2-adamantyl) anisole >
3.1g (9.6mmol) of 3- (2-adamantyl) -5-bromoanisole was placed in a 500mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 100mL of tetrahydrofuran, and the mixture was stirred at-80 ℃. 7.0mL (11mmol) of n-butyllithium (1.6mol/L n-hexane solution) was added dropwise to the solution, and the mixture was stirred under a nitrogen stream for 2 hours. Then, 1.9g (13mmol) of 2-adamantanone was added to the mixture, and the mixture was stirred for 15 hours while gradually raising the temperature back to room temperature.
After stirring, water was added to the mixture, and the aqueous layer was extracted with ethyl acetate. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
The obtained oily substance was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 200mL of methylene chloride, and the mixture was stirred at 0 ℃. To the solution was added 4.6mL (29mmol) of triethylsilane and 7.2mL (57mmol) of boron trifluoride diethyl ether dropwise, and the mixture was stirred for 15 hours while the temperature was raised to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow solid.
Toluene was added to the obtained solid, and the residue was collected by suction filtration to obtain a white solid as the objective substance. This solid was purified by HPLC (developing solvent: chloroform), whereby 1.6g of the objective white solid was obtained in a yield of 45%. The synthesis scheme (a-2) of step 2 is shown below.
[ chemical formula 32]
Figure BDA0002659073460001231
Further, the following shows the utilization of the white solid obtained in the above step 21Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-adamantyl) anisole was obtained.
1H NMR(CDCl3，300MHz)：σ＝6.96(m、1H)、6.74(m、2H)、3.81(s、3H)、2.98(m、2H)、2.44(m、4H)、2.02-1.77(m、22H)、1.57(m、2H)。
< step 3: synthesis of 3, 5-bis (2-adamantyl) phenol >
1.6g (4.4mmol) of 3, 5-bis (2-adamantyl) anisole was placed in a 500mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 120mL of methylene chloride, and the solution was stirred at 0 ℃. To the solution was added dropwise 75mL of boron tribromide (1.0mol/L dichloromethane solution, 75mmol), followed by stirring for 15 hours while the temperature of the solution was raised back to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution at 0 ℃ and the aqueous layer of the resulting mixture was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to obtain 1.6g of a white solid of the objective substance. The synthetic scheme (a-3) of step 3 is shown below.
[ chemical formula 33]
Figure BDA0002659073460001241
Further, the following shows the utilization of the white solid obtained in the above step 31Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-adamantyl) phenol was obtained.
1H NMR(CDCl3，300MHz)：σ＝6.93(m、1H)、6.66(m、2H)、4.51(s、1H)、2.95(m、2H)、2.42(m、4H)、2.02-1.77(m、20H)、1.57-1.53(m、4H)。
< step 4: synthesis of 3, 5-bis (2-adamantyl) phenyltrifluoromethanesulfonic acid >
1.6g (4.4mmol) of 3, 5-bis (2-adamantyl) phenol was placed in a 100mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 40mL of methylene chloride and 2.0mL (14mmol) of triethylamine, and the solution was stirred at 0 ℃. To this, a solution of 1.1mL (6.6mmol) of trifluoromethanesulfonic anhydride in 5mL of dichloromethane was added dropwise, and the mixture was stirred for 15 hours while the temperature was raised back to room temperature.
After stirring, 1N hydrochloric acid was added to the mixture, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a brown oil.
This solid was purified by silica gel column chromatography (developing solvent: hexane) to obtain 2.0g of the desired product as a colorless oil in a yield of 92%. The synthetic scheme (a-4) of step 4 is shown below.
[ chemical formula 34]
Figure BDA0002659073460001251
Further, the following shows the utilization of the white solid obtained in the above step 41Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-adamantyl) phenyltrifluoromethanesulfonic acid was obtained.
1H NMR(CDCl3，300MHz)：σ＝7.35(m、1H)、7.05(m、2H)、3.01(m、2H)、2.43(m、4H)、2.04-1.91(m、10H)、1.78-1.74(m、10H)、1.60-1.56(m、4H)。
< step 5: synthesis of 3, 5-bis (2-adamantyl) -3 ', 5' -di-tert-butyldiphenylamine >
2.0g (4.0mmol) of 3, 5-bis (2-adamantyl) phenyltrifluoromethanesulfonic acid was placed in a 200mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 10mL of tetrahydrofuran, 1.0g (4.9mmol) of 3, 5-di-tert-butylaniline, 1.9g (5.8mmol) of cesium carbonate and 0.13g (0.21mmol) of (. + -.) -2, 2 '-bis (diphenylphosphino) -1, 1' -binaphthyl (abbreviation: (. + -.) -BINAP), the mixture was degassed under reduced pressure, then 30mg (0.13mmol) of palladium (II) acetate was added to the mixture, and the mixture was stirred at 70 ℃ for 21 hours under a nitrogen stream.
After stirring, 500mL of toluene was added to the resulting mixture, and then a filtrate was obtained by suction filtration using magnesium silicate (Japan and Wako pure chemical industries, Ltd.; catalog number: 066- & 05265), diatomaceous earth (Japan and Wako pure chemical industries, Ltd.; catalog number 537- & 02305), and alumina. The resulting filtrate was concentrated to give a reddish brown solid.
This solid was purified by silica gel column chromatography (developing solvent: hexane: toluene ═ 4: 1), and 2.2g of the desired product was obtained as a white solid in a yield of 98%. The synthetic scheme (a-5) of step 5 is shown below.
[ chemical formula 35]
Figure BDA0002659073460001261
Further, the following shows the utilization of the white solid obtained in the above step 51Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-adamantyl) -3 ', 5' -di-tert-butyldiphenylamine was obtained.
1H NMR(CD2Cl2，300MHz)：σ＝6.98-6.97(m、1H)、6.93-6.92(m、5H)、5.77(bs、1H)、2.97(m、2H)、2.42(m、4H)、2.02-1.88(m、14H)、1.78(m、6H)、1.59-1.55(m、4H)、1.30(s、18H)。
< step 6: synthesis of 2Ph-mmAdtBuDPhA2Anth >
0.82g (2.0mmol) of 9, 10-dibromo-2-phenylanthracene, 2.2g (3.9mmol) of 3, 5-bis (2-adamantyl) -3 ', 5 ' -di-tert-butyldiphenylamine, 0.75g (7.8mmol) of sodium tert-butoxide, and 30mg (73. mu. mol) of 2-dicyclohexylphosphino-2 ', 6 ' -dimethoxy-1, 1 ' -biphenyl (abbreviation: SPhos) were placed in a 200mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To the mixture was added 20mL of xylene, the mixture was degassed under reduced pressure, and 20mg (35. mu. mol) of bis (dibenzylideneacetone) palladium (0) was added to the mixture, followed by stirring the mixture at 150 ℃ for 6 hours under a nitrogen stream.
After stirring, 500mL of toluene was added to the resulting mixture, and then a filtrate was obtained by suction filtration using magnesium silicate (Japan and Wako pure chemical industries, Ltd.; catalog number: 066- & 05265), diatomaceous earth (Japan and Wako pure chemical industries, Ltd.; catalog number 537- & 02305), and alumina. The resulting filtrate was concentrated to give a brown solid.
This solid was purified by silica gel column chromatography (developing solvent: hexane: toluene ═ 9: 1) to obtain the desired product as a yellow solid. The obtained yellow solid was recrystallized from ethyl acetate and ethanol to obtain the objective yellow solid. The obtained yellow solid was purified by High Performance Liquid Chromatography (HPLC) to obtain 0.29g of the objective yellow solid in a yield of 11%. The synthetic scheme (a-6) of step 6 is shown below.
[ chemical formula 36]
Figure BDA0002659073460001281
0.29g of the yellow solid obtained was purified by sublimation by gradient sublimation. Sublimation purification was carried out by heating the yellow solid at 300 ℃ for 15 hours under a pressure of 3.3 Pa. After purification by sublimation, 0.22g of the objective substance was obtained as a yellow solid in a recovery rate of 76%.
Further, the following shows the utilization of the yellow solid obtained in the above step 6 1Measurement result of H NMR. Further, FIG. 14 shows1H NMR spectrum. From the results, 2Ph-mmAdtBuDPhA2Anth (structural formula (100)) was obtained.
1H NMR(CD2Cl2，300MHz)：σ＝8.39-8.37(m、1H)、8.26-8.11(m、3H)、7.62-7.54(m、1H)、7.43-7.25(m、7H)、7.04-6.92(m、12H)、2.89-2.86(m、4H)、2.21-2.16(m、8H)、1.87-1.57(m、40H)、1.46-1.27(m、8H)、1.15-1.13(m、36H)。
Next, the absorption spectrum and emission spectrum of a toluene solution of 2Ph-mmAdtBuDPhA2Anth were measured. Ultraviolet-visible absorption spectrum (hereinafter referred to as "absorption spectrum") and emission spectrum were measured. For the measurement of the absorption spectrum, an ultraviolet-visible spectrophotometer (model V550 manufactured by japan spectrophotometers) was used. In the measurement of the emission spectrum, a fluorescence spectrophotometer (FP-8600 DS manufactured by Nippon spectral Co., Ltd.) was used. Fig. 15 shows the measurement results of the absorption spectrum and the emission spectrum of the obtained toluene solution. The horizontal axis represents wavelength and the vertical axis represents absorption intensity.
As is clear from FIG. 15, the toluene solution of 2Ph-mmAdtBuDPhA2Anth had an absorption peak at around 492nm and an emission peak at 539nm (excitation wavelength of 460 nm).
Example 2
In this example, a light-emitting device was manufactured using the compound of one embodiment of the present invention and operating characteristics were measured. The light emitting devices shown in this embodiment are the light emitting device 1-1, the light emitting device 1-2, the light emitting device 1-3, the light emitting device 1-4, and the light emitting device 1-5. These light-emitting devices have the device structure shown in fig. 16 and the structure described in < structure example 5> of light-emitting layer of embodiment mode 2, specifically, the structure shown in table 1. These light-emitting devices differ only in the content of the compound according to one embodiment of the present invention, i.e., N '-bis [3, 5-bis (2-adamantyl) phenyl ] -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviated as 2 Ph-mmadtudpha 2 anthh), contained in the light-emitting layer of the light-emitting device, but the other structures are the same. Further, as a comparative example of these light-emitting devices, use of TTPA) was shown instead of the compound of one embodiment of the present invention contained in the light-emitting layer of the light-emitting device, i.e., comparative light-emitting device 1-a of 2 Ph-mmaddbaudpha 2 anthh. The chemical formula of the material used in this example is shown below.
[ Table 1]
Figure BDA0002659073460001301
* mPCCzPTzn-02∶PCCP∶[Ir(PPy)2(mdppy)]∶2Ph-mmAdtBuDPhA2Anth(0.5∶0.5∶0.1∶0.01 40nm)
** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmAdtBuDPhA2Anth(0.5∶0.5∶0.1∶0.025 40nm)
*** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmAdtBuDPhA2Anth(0.5∶0.5∶0.1∶0.05 40nm)
**** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmAdtBuDPhA2Anth(0.5∶0.5∶0.1∶0.1 40nm)
***** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)](0.5∶0.5∶0.1 40nm)
****** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶TTPA(0.5∶0.5∶0.1∶0.05 40nm)
[ chemical formula 37]
Figure BDA0002659073460001311
Structure of light emitting device
As shown in fig. 16, the light emitting device shown in this embodiment has the following structure: a hole injection layer 911, a hole transport layer 912, a light-emitting layer 913, an electron transport layer 914, and an electron injection layer 915 which constitute an EL layer 902 are sequentially stacked over a first electrode 901 formed over a substrate 900, and a second electrode 903 is stacked over the electron injection layer 915.
The substrate 900 uses a glass substrate. In addition, the first electrode 901 uses an indium tin oxide (ITSO) film containing silicon oxide and has a thickness of 70 nm. Further, the electrode area of the first electrode 901 is 4mm2(2mm×2mm)。
The hole injection layer 911 was formed using a film of 4, 4', 4 ″ - (benzene-1, 3, 5-triyl) tris (dibenzothiophene) (abbreviated as DBT3P-II) and molybdenum oxide at a mass ratio of DBT3P-II to molybdenum oxide of 1: 0.5, and had a thickness of 40 nm.
The hole-transporting layer 912 was made of 4, 4 '-diphenyl-4' - (9-phenyl-9H-carbazol-3-yl) triphenylamine (abbreviated as PCBBi1BP) and had a thickness of 20 nm.
The light-emitting layer 913 of the light-emitting devices 1-1 to 1-4 uses a light-emitting layer containing 9- [3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl group]-9 ' -phenyl-2, 3 ' -bi-9H-carbazole (abbreviated as mPCzPTzn-02), 3 ' -bis (9-phenyl-9H-carbazole) (abbreviated as PCCP), [2- (4-methyl-5-phenyl-2-pyridyl-. kappa.N) phenyl-. kappa.C ]Bis [2- (2-pyridyl-. kappa.N) phenyl-. kappa.C]Iridium (abbreviation: [ Ir (ppy)2(mdppy)]) And a film of 2Ph-mmAdtBuDPhA2Anth, 40nm in thickness. Further, the light-emitting layer 913 of the light-emitting devices 1 to 5 includes mPCzPTzn-02, PCCP and [ Ir (ppy)2(mdppy)]And a film not containing 2Ph-mmAdtBuDPhA2Anth, having a thickness of 40 nm. Further, the light-emitting layer 913 of the comparative light-emitting device 1-a used a light-emitting layer containing mPCzPTzn-02, PCCP, [ Ir (ppy)2(mdppy)]And a film of TTPA having a thickness of 40 nm. The light-emitting layers 913 of the respective light-emitting devices have the weight ratios shown in table 1, respectively.
The electron transport layer 914 used was a laminate film of mPCzPTzn-02 having a thickness of 20nm and 2, 9-bis (naphthalene-2-yl) -4, 7-diphenyl-1, 10-phenanthroline (NBphen for short) having a thickness of 10 nm.
The electron injection layer 915 uses lithium fluoride (LiF) and has a thickness of 1 nm.
In addition, aluminum was used for the second electrode 903, and the thickness was 200 nm. In the present embodiment, the second electrode 903 serves as a cathode.
Operating characteristics of light-emitting device
The operating characteristics of the fabricated light emitting device were tested. In the measurement of luminance, CIE chromaticity and Electroluminescence (EL) spectrum, a spectroradiometer (SR-UL 1R manufactured by Topcon Tehnohouse Co., Ltd.) was used. The test was carried out at room temperature (atmosphere maintained at 23 ℃).
As the measurement results of the operation characteristics of the light emitting devices 1-1 to 1-5 manufactured in the present embodiment, fig. 17 to 20 respectively show a current density-luminance characteristic, a voltage-luminance characteristic, a luminance-current efficiency characteristic, and a voltage-current density characteristic.
FIG. 21 shows the signal at 2.5mA/cm2The current density of (a) is an electroluminescence spectrum (EL spectrum) when a current flows through each light emitting device.
Table 2 shows 1000cd/m2Main initial characteristic values of the respective light emitting devices in the vicinity.
[ Table 2]
Figure BDA0002659073460001341
The light-emitting devices 1-1 to 1-4 are devices in which a compound according to one embodiment of the present invention, i.e., 2 Ph-mmadtudpha 2 ath, is added to the light-emitting device 1-5. As shown in FIG. 21, the EL spectra of the light-emitting devices 1 to 5 showed a peak wavelength of 522nm derived from [ Ir (ppy)2(mdppy)]The green color of (2) emits light. Further, the EL spectra of the light-emitting devices 1-1 to 1-4 showed green luminescence derived from 2Ph-mmAdtBuDPhA2Anth with a peak wavelength of about 545 nm. From this, it is known that in the light-emitting devices 1-1 to 1-4, 2 Ph-mmadbtbha 2 anthh as a fluorescent light-emitting substance receives excitation energy to emit light. Further, the above results show that of the light emitting device 1-1 to the light emitting device 1-5The external quantum efficiency is as high as more than 21%. Here, since the maximum generation probability of the singlet excitons generated by the recombination of the carriers (holes and electrons) injected from the pair of electrodes is 25%, the maximum external quantum efficiency of the fluorescent light-emitting device is 7.5% when the light extraction efficiency to the outside is 30%. However, external quantum efficiencies of more than 7.5% were obtained in the light emitting devices 1-1 to 1-4. This is because: the fluorescent substance can emit light from singlet excitons generated by recombination of carriers (holes and electrons) injected from a pair of electrodes, and also from energy transfer of triplet excitons.
It can also be known that: in comparison between the light-emitting devices 1-1 to 1-5 in which the concentrations of 2Ph-mmAdtBuDPhA2Anth contained in the light-emitting layers were different, the light-emitting devices 1-1 to 1-5 all had equivalent external quantum efficiencies. Thus, the compound according to one embodiment of the present invention, i.e., 2 Ph-mmadtudpha 2 ath, can suppress deactivation of triplet excitation energy which is particularly significant when the light-emitting layer of the light-emitting device has a high concentration, and can emit light with high efficiency. Further, in the comparison of the light-emitting device 1-3 with the comparative light-emitting device 1-a, the comparative light-emitting device 1-a whose light-emitting layer contains TTPA at the same concentration as 2Ph-mmAdtBuDPhA2Anth contained in the light-emitting device 1-3 has an external quantum efficiency of half or less of that of the light-emitting device 1-3. This means that: compared with TTPA without a protecting group used for the comparative light-emitting device 1-a, 2 Ph-mmadbtbha 2 antrh used for the light-emitting device 1-3 can suppress transfer of triplet excitation energy from the host by the dexter mechanism due to the protecting group, and can efficiently convert both the singlet excitation energy and the triplet excitation energy into light emission, which has a large influence on external quantum efficiency.
Further, 50mA/cm was applied to each of the light emitting devices 1-1 to 1-5 2A constant current density drive test was performed. Fig. 33 shows the results. From the results, it is understood that the reliability is improved when the concentration of the guest 2Ph-mmAdtBuDPhA2Anth is increased. This means that: when the guest concentration in the light-emitting layer is increased, the excitation energy in the light-emitting layer can be efficiently converted into light emission of the guest. That is, when the guest concentration is increased, the concentration of the guest can be increasedThe energy transfer from the host to the guest based on the Dexter mechanism is made while the triplet excitation energy transfer speed from the host to the guest based on the Foster mechanism is increased. Therefore, a light-emitting device using the compound of one embodiment of the present invention has good light-emitting efficiency and reliability.
Example 3
In this example, a light-emitting device was manufactured using the compound of one embodiment of the present invention and operating characteristics were measured. The light emitting devices shown in this embodiment are the light emitting device 2-1, the light emitting device 2-2, the light emitting device 2-3, the light emitting device 2-4, and the light emitting device 2-5. These light-emitting devices have the device structure shown in fig. 16 and the structure described in < structure example 3> of light-emitting layer of embodiment mode 2, specifically, the structure shown in table 3. These light-emitting devices have different contents of the compound according to one embodiment of the present invention, i.e., N '-bis [3, 5-bis (2-adamantyl) phenyl ] -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviated as 2 Ph-mmadtudpha 2 anthh), contained in the light-emitting layer, but the other structures are the same. Further, as a comparative example of these light-emitting devices, a comparative light-emitting device 2-a using TTPA instead of the compound of one embodiment of the present invention included in the light-emitting layer of the light-emitting device, i.e., 2 Ph-mmaddbaudpha 2 anthh is shown. The chemical formula of the material used in this example is shown below.
[ Table 3]
Figure BDA0002659073460001361
* 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmAdtBuDPhA2Anth(0.8∶0.2∶0.01 40nm)
** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmAdtBuDPhA2Anth(0.8∶0.2∶0.025 40nm)
*** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmAdtBuDPhA2Anth(0.8∶0.2∶0.05 40nm)
**** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmAdtBuDPhA2Anth(0.8∶0.2∶0.1 40nm)
***** 4，6mCzP2Pm∶[Ir(ppz)3](0.8∶0.2 40nm)
****** 4，6mCzP2Pm∶[Ir(ppz)3]∶TTPA(0.8∶0.2∶0.1 40nm)
[ chemical formula 38]
Figure BDA0002659073460001371
Structure of light emitting device
The light-emitting device shown in this embodiment has a structure shown in fig. 16, as in embodiment 2. The structure of the light emitting device shown in this embodiment is different from that of embodiment 2 in that: in the light-emitting device 2-1, the light-emitting device 2-2, the light-emitting device 2-3, the light-emitting device 2-4, and the light-emitting device 2-5, 3' -bis (9-phenyl-9H-carbazole) (PCCP for short) is used for the hole-transporting layer 912, and tris [2- (1H-pyrazol-1-yl-. kappa.n ] is used for the light-emitting layer 9132) Phenyl-kappa C]Iridium (III) (abbreviation: [ Ir (ppz))3]) And 9, 9' - (pyrimidine-4, 6-diylbis-3, 1-phenylene) bis (9H-carbazole) (abbreviation: 4, 6mCzP2Pm), and electron transport layer 914 uses 4, 6mCzP2 Pm.
Operating characteristics of light-emitting device
The operating characteristics of the fabricated light emitting device were tested. The test method is the same as in example 2, and thus the description is omitted.
As the measurement results of the operation characteristics of the light emitting devices 2-1 to 2-5 manufactured in the present embodiment, fig. 22 to 25 respectively show a current density-luminance characteristic, a voltage-luminance characteristic, a luminance-current efficiency characteristic, and a voltage-current density characteristic.
FIG. 26 shows the signal at 2.5mA/cm2The current density of (a) is an electroluminescence spectrum (EL spectrum) when a current flows through each light emitting device.
Table 4 shows 1000cd/m2Main initial characteristic values of the respective light emitting devices in the vicinity.
[ Table 4]
Figure BDA0002659073460001391
The light-emitting devices 2-1 to 2-4 are devices in which a compound which is one embodiment of the present invention, i.e., 2 Ph-mmadtudpha 2 ath, is added to the light-emitting device 2-5. As shown in FIG. 26, the EL spectra of the light-emitting devices 2 to 5 showed peaks at 531nm and originated from 4, 6mCZP2Pm and [ Ir (ppz) ]3]Does not originate from 4, 6mCZP2Pm and [ Ir (ppz)3]Green luminescence of the emission spectra respectively present. Further, the EL spectra of the light-emitting devices 2-1 to 2-4 showed green luminescence derived from 2Ph-mmAdtBuDPhA2Anth with a peak wavelength of about 545 nm. From this, it is known that in the light-emitting devices 2-1 to 2-4, 2 Ph-mmaddgudpha 2Anth as a fluorescent light-emitting substance receives excitation energy to emit light. In addition, the above results indicate that the external quantum efficiencies of the light emitting devices 2-1 to 2-5 are all as high as 19% or more. Here, since the maximum generation probability of the singlet excitons generated by the recombination of the carriers (holes and electrons) injected from the pair of electrodes is 25%, the maximum external quantum efficiency of the fluorescent light-emitting device is 7.5% when the light extraction efficiency to the outside is 30%. However, external quantum efficiencies of more than 7.5% were obtained in the light emitting devices 2-1 to 2-4. This is because: the fluorescent light-emitting substance can emit light from singlet excitons generated by recombination of carriers (holes and electrons) injected from a pair of electrodes, and also can emit light from energy transfer of triplet excitons or light from singlet excitons generated from triplet excitons through intersystem crossing in an exciplex.
It can also be known that: in comparison between the light-emitting devices 2-1 to 2-5 in which the concentrations of 2Ph-mmAdtBuDPhA2Anth contained in the light-emitting layers were different, the light-emitting devices 2-1 to 2-5 all had equivalent external quantum efficiencies. Thus, the compound according to one embodiment of the present invention, i.e., 2 Ph-mmadtudpha 2 ath, can suppress deactivation of triplet excitation energy which is particularly significant when the light-emitting layer of the light-emitting device has a high concentration, and can emit light with high efficiency. Further, in the comparison of the light-emitting device 2-3 with the comparative light-emitting device 2-a, the comparative light-emitting device 2-a whose light-emitting layer contains TTPA at the same concentration as 2Ph-mmAdtBuDPhA2Anth contained in the light-emitting device 2-3 has an external quantum efficiency of half or less of that of the light-emitting device 2-3. This means that: compared with TTPA without a protecting group used for the comparative light-emitting device 2-a, 2 Ph-mmadbtbha 2 antrh used for the light-emitting device 2-3 can suppress transfer of triplet excitation energy from the host by the dexter mechanism due to the protecting group, and can efficiently convert both the singlet excitation energy and the triplet excitation energy into light emission, which has a large influence on external quantum efficiency.
CV measurement results
Subsequently, 4, 6mCZP2Pm and [ Ir (ppz) ] used in the light-emitting layer of each light-emitting device were subjected to Cyclic Voltammetry (CV) 3]The electrochemical characteristics (oxidation reaction characteristics and reduction reaction characteristics) of (a). The following describes the measurement method.
As a measuring device, an electrochemical analyzer (ALS model 600A or 600C manufactured by BAS inc.). Furthermore, as the solvent, dehydrated Dimethylformamide (DMF) (99.8%, catalog number: 22705-6, manufactured by Aldrich Co., Ltd.) was used, and tetra-n-butylammonium perchlorate (n-Bu) as a supporting electrolyte was used4NClO4) (manufactured by Tokyo Chemical Industry co., Ltd.) catalog No.: t0836) was dissolved at a concentration of 100mmol/L, and the object to be measured was dissolved at a concentration of 2mmol/L to prepare a solution. Further, a platinum electrode (manufactured by BAS inc., PTE platinum electrode) was used as the working electrode, a platinum electrode (manufactured by BAS inc., Pt counter electrode (5cm) for VC-3) was used as the auxiliary electrode, and an Ag/Ag + electrode (manufactured by BAS inc., RE7 non-aqueous solution type reference electrode) was used as the reference electrode. Furthermore, CV measurement was performed at room temperature (20 ℃ C. to 25 ℃ C.). The scanning speed during CV measurement was set to 0.1V/sec, and the oxidation potential Ea [ V ] with respect to the reference electrode was measured]And a reduction potential Ec [ V ]]. Ea is the intermediate potential between the oxidation-reduction waves and Ec is the intermediate potential between the reduction-oxidation waves. Here, it is known that the potential energy of the reference electrode used in the present embodiment with respect to the vacuum level is-4.94 [ eV [ ] ]Thus making use of the HOMO level [ eV](ii) LUMO energy level [ eV ] of-4.94-Ea]The HOMO level and the LUMO level can be determined by two equations of-4.94-Ec, respectively.
As a result of CV measurement, 4, 6mCZP2Pm had an oxidation potential of 0.95V and a reduction potential of-2.06V. Further, calculation was based on CV measurementThe HOMO level of the 4, 6mCZP2Pm is-5.89 eV, and the LUMO level is-2.88 eV. Further, [ Ir (ppz)3]The oxidation potential of (A) was 0.45V, and the reduction potential was-3.17V. In addition, [ Ir (ppz) ] calculated according to CV measurement3]The HOMO level of (A) is-5.39 eV, and the LUMO level is-1.77 eV.
As described above, 4, 6mCZP2Pm has a LUMO energy level lower than [ Ir (ppz) ]3]LUMO energy level of [ Ir (ppz) ]3]Is higher than the HOMO level of 4, 6mCzP2 Pm. Thus, when the compound is used in a light-emitting layer, electrons and holes can be efficiently injected into 4, 6mCZP2Pm and [ Ir (ppz) ], respectively3]So that 4, 6mCZP2Pm and [ Ir (ppz)3]An exciplex is formed. In addition, the emission energy of the EL spectrum of the light-emitting devices 2 to 5 shown in fig. 26 was compared with the HOMO level of 4, 6mCzP2Pm and [ ir (ppz) ]3]The difference in LUMO energy levels of (A) was close to each other, and it was found that the luminescence originated from 4, 6mCZP2Pm and [ Ir (ppz)3]Luminescence of the exciplex formed.
Further, 50mA/cm was applied to each of the light emitting devices 2-1 to 2-52A constant current density drive test was performed. Fig. 34 shows the result thereof. From the results, it is understood that the reliability is improved when the concentration of the guest 2Ph-mmAdtBuDPhA2Anth is increased. This means that: when the guest concentration in the light-emitting layer is increased, the excitation energy in the light-emitting layer can be efficiently converted into light emission of the guest. That is, in the case of increasing the concentration of the guest, the energy transfer rate of triplet excitation energy based on the forster mechanism from the host to the guest can be increased while suppressing the energy transfer based on the dexter mechanism from the host to the guest. Therefore, a light-emitting device using the compound of one embodiment of the present invention has good light-emitting efficiency and reliability.
Example 4
Synthesis example 2
In this example, a method for synthesizing a compound of one embodiment of the present invention represented by the structural formula (102) of embodiment 1, that is, N '-bis [3, 5-bis (2-adamantyl) phenyl ] -N, N' -bis [3, 5-bis (3, 5-di-tert-butylphenyl) phenyl ] -2-phenylanthracene-9, 10-diamine (abbreviated as 2 Ph-mmadbu dpha2 nth-02) will be described. The structure of 2Ph-mmAdtBuDPhA2Anth-02 is shown below.
[ chemical formula 39]
Figure BDA0002659073460001431
< step 1: synthesis of 3, 5-bis (2-adamantyl) -3 ', 5' -bis (3, 5-di-t-butylphenyl) diphenylamine >
3.6g (7.2mmol) of 3, 5-bis (2-adamantyl) phenyltrifluoromethanesulfonic acid was placed in a 200mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 20mL of tetrahydrofuran, 3.7g (4.9mmol) of bis (3, 5-di-t-butylphenyl) aniline, 3.3g (10mmol) of cesium carbonate and 0.40g (0.64mmol) of (. + -.) -2, 2 '-bis (diphenylphosphino) -1, 1' -binaphthyl (abbreviation: (. + -.) -BINAP), the mixture was degassed under reduced pressure, then 0.10g (0.45mmol) of palladium (II) acetate was added to the mixture, and the mixture was stirred at 70 ℃ for 37 hours under a nitrogen stream.
After stirring, 500mL of toluene was added to the resulting mixture, and then a filtrate was obtained by suction filtration using magnesium silicate (Japan and Wako pure chemical industries, Ltd.; catalog number: 066- & 05265), diatomaceous earth (Japan and Wako pure chemical industries, Ltd.; catalog number 537- & 02305), and alumina. The resulting filtrate was concentrated to give a reddish brown solid.
This solid was purified by silica gel column chromatography (developing solvent: hexane: toluene ═ 4: 1) to obtain a yellowish white solid. The obtained yellowish white solid was recrystallized from toluene to obtain 3.5g of a desired white solid in a yield of 59%. The synthesis scheme (b-1) of step 1 is shown below.
[ chemical formula 40]
Figure BDA0002659073460001441
Further, the following shows the utilization of the white solid obtained in the above step 11Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-adamantyl)-3 ', 5' -bis (3, 5-di-tert-butylphenyl) diphenylamine.
1H NMR(CD2Cl2，300MHz)：σ＝7.46-7.44(m，6H)，7.27-7.26(m，1H)，7.22-7.21(m，2H)，7.05(s，2H)，7.02(s，1H)，6.00(bs，1H)，3.01(m，2H)，2.45(m，4H)，2.03-1.76(m，20H)，1.57-1.52(m，4H)，1.37(s，36H)。
< step 2: synthesis of 2Ph-mmAdtBuDPhA2Anth-02 >
In a 200mL three-necked flask, 0.87g (2.1mmol) of 9, 10-dibromo-2-phenylanthracene, 3.5g (4.2mmol) of 3, 5-bis (2-adamantyl) -3 ', 5 ' -bis (3, 5-di-t-butylphenyl) diphenylamine, 0.81g (8.4mmol) of sodium t-butoxide, and 60mg (0.15mmol) of 2-dicyclohexylphosphino-2 ', 6 ' -dimethoxy-1, 1 ' -biphenyl (abbreviated as SPhos) were placed, and the air in the flask was replaced with nitrogen. To the mixture was added 25mL of xylene, the mixture was degassed under reduced pressure, 40mg (70. mu. mol) of bis (dibenzylideneacetone) palladium (0) was added to the mixture, and the mixture was stirred at 150 ℃ for 6 hours under a nitrogen stream.
After stirring, 500mL of toluene was added to the resulting mixture, and then a filtrate was obtained by suction filtration using magnesium silicate (Japan and Wako pure chemical industries, Ltd.; catalog number: 066- & 05265), diatomaceous earth (Japan and Wako pure chemical industries, Ltd.; catalog number 537- & 02305), and alumina. The resulting filtrate was concentrated to give a brown solid.
This solid was purified by silica gel column chromatography (developing solvent: hexane: toluene ═ 9: 1) to obtain the desired product as a yellow solid. The obtained yellow solid was purified by High Performance Liquid Chromatography (HPLC) to obtain 0.57g of the desired product as a yellow solid in a yield of 14%. The synthesis scheme (b-2) of step 2 is shown below.
[ chemical formula 41]
Figure BDA0002659073460001461
0.39g of the yellow solid obtained is sublimed to purity by the gradient sublimation methodAnd (4) transforming. At a pressure of 4.0X 10-2Sublimation purification was carried out by heating the yellow solid at 360 ℃ for 15 hours under Pa. After purification by sublimation, 0.34g of the objective substance was obtained as a yellow solid in a recovery rate of 87%.
Further, the following shows the utilization of the yellow solid obtained in the above step 21Measurement result of H NMR. Further, FIG. 27 shows1H NMR spectrum. From the results, it was found that 2Ph-mmAdtBuDPhA2Anth-02 (structural formula (102)) was obtained.
1H NMR(CD2Cl2，300MHz)：σ＝8.56-8.52(m，1H)，8.44-8.29(m，3H)，7.69-7.62(m，1H)，7.48-7.12(m，28H)，7.05(m，2H)，6.90(m，1H)，2.94-2.82(m，4H)，2.24-2.02(m，8H)，1.88-1.05(m，120H)。
FIG. 28 shows the results of measurement of the absorption spectrum and emission spectrum of a toluene solution of 2Ph-mmAdtBuDPhA2 Anth-02. The measurement method was the same as that shown in example 1.
As is clear from FIG. 28, the toluene solution of 2Ph-mmAdtBuDPhA2Anth-02 had an absorption peak near 485nm and a peak of light emission wavelength was 537nm (excitation wavelength: 460 nm).
Example 5
Synthesis example 3
In this example, a method for synthesizing a compound of one embodiment of the present invention represented by the structural formula (116) of embodiment 1, i.e., N '-bis {3, 5-bis (2-bicyclo [2.2.1] heptyl) phenyl } -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviated as 2 Ph-mmnbtbudpadpha 2 anthh) is described. The structure of 2Ph-mmnbtBuDPhA2Anth is shown below.
[ chemical formula 42]
Figure BDA0002659073460001481
The above-mentioned 2Ph-mmnbtBuDPhA2Anth can be synthesized in the same manner as in example 1 by using 2-norborneone instead of the 2-adamantanone used in step 1 and step 2 of example 1 and using the methods shown in the following synthesis scheme (c-1), synthesis scheme (c-2), synthesis scheme (c-3), synthesis scheme (c-4), synthesis scheme (c-5) and synthesis scheme (c-6).
< step 1: synthesis of 3- (2-bicyclo [2.2.1] heptyl) -5-bromoanisole >
6.7g (25mmol) of 3, 5-dibromoanisole was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 240mL of tetrahydrofuran, and the mixture was stirred at-80 ℃. 17mL (27mmol) of n-butyllithium (1.6mol/L n-hexane solution) was added dropwise to the solution, and the mixture was stirred under a nitrogen stream for 2 hours. Then, 3.4g (31mmol) of 2-norborneone was added to the mixture, and the mixture was stirred for 15 hours while gradually returning the temperature to room temperature.
After stirring, water was added to the mixture, and the aqueous layer was extracted with ethyl acetate. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
The obtained oily substance was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 200mL of methylene chloride, and the mixture was stirred at 0 ℃. To the solution was added 12mL (75mmol) of triethylsilane and 19mL (0.15mol) of boron trifluoride diethyl ether dropwise, and the mixture was stirred for 15 hours while the temperature was raised to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
This oil was purified by silica gel column chromatography (hexane: toluene ═ 4: 1 as a developing solvent) to obtain the desired colorless oil. The obtained solid was purified by HPLC (developing solvent: chloroform), whereby 4.7g of the objective compound was obtained as a colorless oil in a yield of 66%. The synthesis scheme (c-1) of step 1 is shown below.
[ chemical formula 43]
Figure BDA0002659073460001501
Further, the following shows the utilization of the white solid obtained in the above step 11Measurement result of H NMR. From the results, it was found that 3- (2-bicyclo [2.2.1] was obtained]Heptyl) -5-bromoanisole.
1H NMR(CDCl3，300MHz)：σ＝6.96(s，1H)，6.87(m，1H)，6.70(s，1H)，3.78(s，3H)，3.18-3.11(m，1H)，2.40-2.32(m，2H)，2.00-1.89(m，1H)，1.57-1.18(m，7H)。
< step 2: synthesis of 3, 5-bis (2-bicyclo [2.2.1] heptyl) anisole >
4.7g (17mmol) of 3- (2-bicyclo [2.2.1] heptyl) -5-bromoanisole was placed in a 500mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 160mL of tetrahydrofuran, and the mixture was stirred at-80 ℃. 11mL (18mmol) of n-butyllithium (1.6mol/L n-hexane solution) was added dropwise to the solution, and the mixture was stirred under a nitrogen stream for 3 hours. Then, 2.2g (20mmol) of 2-norborneone was added to the mixture, and the mixture was stirred for 15 hours while gradually returning the temperature to room temperature.
After stirring, water was added to the mixture, and the aqueous layer was extracted with ethyl acetate. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
The obtained oily substance was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 150mL of methylene chloride, and the mixture was stirred at 0 ℃. To the solution was added 8.0mL (50mmol) of triethylsilane and 12mL (96mmol) of boron trifluoride diethyl ether dropwise, and the mixture was stirred for 15 hours while the temperature was raised to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
This oil was purified by silica gel column chromatography (developing solvent hexane: toluene ═ 4: 1) to give a colorless oil. The obtained oil was purified by HPLC (developing solvent: chloroform), whereby 3.4g of the objective colorless oil was obtained in a yield of 69%. The synthesis scheme (c-2) of step 2 is shown below.
[ chemical formula 44]
Figure BDA0002659073460001511
Further, the following shows the utilization of the white solid obtained in the above step 21Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-bicyclo [2.2.1] was obtained]Heptyl) anisole.
1H NMR(CDCl3，300MHz)：σ＝6.69(m，1H)，6.59(m，2H)，3.80(s，3H)，3.22-3.16(m，2H)，2.40-2.30(m，4H)，2.00-1.90(m，2H)，1.59-1.19(m，14H)。
< step 3: synthesis of 3, 5-bis (2-bicyclo [2.2.1] heptyl) phenol >
3.4g (11mmol) of 3, 5-bis (2-bicyclo [2.2.1] heptyl) anisole was placed in a 300mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 100mL of methylene chloride, and the solution was stirred at 0 ℃. To the solution was added dropwise 23mL of boron tribromide (1.0mol/L of a dichloromethane solution, 23mmol), followed by stirring for 15 hours while the temperature of the solution was raised back to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution, and the aqueous layer of the resulting mixture was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to obtain 3.1g of a white solid of the objective substance. The synthesis scheme (c-3) of step 3 is shown below.
[ chemical formula 45]
Figure BDA0002659073460001521
Further, the following shows the utilization of the white solid obtained in the above step 31Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-bicyclo [2.2.1] was obtained]Heptyl) phenol.
1H NMR(CDCl3，300MHz)：σ＝6.67(m，1H)，6.52(m，2H)，4.56(bs，1H)，3.20-3.13(m，2H)，2.38-2.31(m，4H)，1.99-1.89(m，2H)，1.74-1.18(m，14H)。
< step 4: synthesis of 3, 5-bis (2-bicyclo [2.2.1] heptyl) phenyltrifluoromethanesulfonic acid >
3.1g of 3, 5-bis (2-bicyclo [2.2.1] heptyl) phenol was placed in a 300mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 100mL of methylene chloride and 5.0mL (36mmol) of triethylamine, and the solution was stirred at 0 ℃. To this was added dropwise a solution of 3.0mL (18mmol) of trifluoromethanesulfonic anhydride in 10mL of dichloromethane, and the mixture was stirred for 15 hours while the temperature was raised back to room temperature.
After stirring, 1N hydrochloric acid was added to the mixture, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a brown oil.
This oil was purified by silica gel column chromatography (developing solvent: hexane) to obtain 3.8g of the objective colorless oil in an overall yield of 80% (step 3 and step 4). The synthetic scheme (c-4) of step 4 is shown below.
[ chemical formula 46]
Figure BDA0002659073460001531
Further, the following shows the utilization of the white solid obtained in the above step 41Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-bicyclo [2.2.1] was obtained]Heptyl) phenyltrifluoromethanesulfonic acid.
1H NMR(CDCl3，300MHz)：σ＝7.06(m，1H)，6.91(m，2H)，3.26-3.19(m，2H)，2.41-2.33(m，4H)，2.05-1.95(m，2H)，1.60-1.17(m，14H)。
< step 5: synthesis of 3, 5-bis (2-bicyclo [2.2.1] heptyl) -3 ', 5' -di-tert-butyldiphenylamine >
3.8g (9.0mmol) of 3, 5-bis (2-bicyclo [2.2.1] heptyl) phenyltrifluoromethanesulfonic acid was placed in a 200mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 20mL of tetrahydrofuran, 2.2g (11mmol) of 3, 5-di-tert-butylaniline, 4.1g (13mmol) of cesium carbonate and 0.75g (1.2mmol) of (. + -.) -2, 2 '-bis (diphenylphosphino) -1, 1' -BINAP (abbreviation:. (. + -.) -BINAP), the mixture was degassed under reduced pressure, then 0.18g (0.80mmol) of palladium (II) acetate was added to the mixture, and the mixture was stirred at 70 ℃ for 18 hours under a nitrogen stream.
After stirring, 400mL of toluene was added to the resulting mixture, and then a filtrate was obtained by suction filtration using magnesium silicate (Japan and Wako pure chemical industries, Ltd.; catalog number: 066- & 05265), diatomaceous earth (Japan and Wako pure chemical industries, Ltd.; catalog number 537- & 02305), and alumina. The resulting filtrate was concentrated to give a reddish brown solid.
This solid was purified by silica gel column chromatography (developing solvent: hexane: toluene ═ 4: 1), and 1.7g of the desired product was obtained as a white solid in a yield of 39%. The synthetic scheme (c-5) of step 5 is shown below.
[ chemical formula 47]
Figure BDA0002659073460001541
Further, the following shows the utilization of the white solid obtained in the above step 51Measurement result of H NMR. From the results, it was found that 3, 5-bis (2-bicyclo [2.2.1] was obtained]Heptyl) -3 ', 5' -di-tert-butyldiphenylamine.
1H NMR(CD2Cl2，300MHz)：σ＝6.99(m，1H)，6.94(m，2H)，6.76(m，2H)，6.66(m，1H)，5.76(bs，1H)，3.20-3.13(m，2H)，2.39-2.30(m，4H)，1.99-1.88(m，2H)，1.59-1.44(m，4H)，1.45-1.19(m，28H)。
< step 6: synthesis of 2Ph-mmnbtBuDPhA2Anth >
In a 200mL three-necked flask, 0.72g (1.7mmol) of 9, 10-dibromo-2-phenylanthracene, 1.7g (3.5mmol) of 3, 5-bis (2-bicyclo [2.2.1] heptyl) -3 ', 5 ' -di-t-butyldiphenylamine, 0.67g (7.0mmol) of sodium t-butoxide, and 60mg (0.15mmol) of 2-dicyclohexylphosphino-2 ', 6 ' -dimethoxy-1, 1 ' -biphenyl (abbreviated as: SPhos) were placed, and the atmosphere in the flask was replaced with nitrogen. 20mL of xylene was added to the mixture, the mixture was degassed under reduced pressure, 40mg (70. mu. mol) of bis (dibenzylideneacetone) palladium (0) was added to the mixture, and the mixture was stirred at 150 ℃ for 3 hours under a nitrogen stream.
After stirring, 500mL of toluene was added to the resulting mixture, and then a filtrate was obtained by suction filtration using magnesium silicate (Japan and Wako pure chemical industries, Ltd.; catalog number: 066- & 05265), diatomaceous earth (Japan and Wako pure chemical industries, Ltd.; catalog number 537- & 02305), and alumina. The resulting filtrate was concentrated to give a brown solid.
This solid was purified by silica gel column chromatography (developing solvent: hexane: toluene ═ 9: 1) to obtain the desired product as a yellow solid. The obtained yellow solid was purified by High Performance Liquid Chromatography (HPLC) to obtain 0.51g of the objective yellow solid in a yield of 25%. The synthetic scheme (c-6) of step 6 is shown below.
[ chemical formula 48]
Figure BDA0002659073460001561
0.45g of the yellow solid obtained was purified by sublimation by gradient sublimation. Sublimation purification was carried out by heating the yellow solid at 275 ℃ for 15 hours under a pressure of 3.5 Pa. After purification by sublimation, 0.30g of the objective substance was obtained as a yellow solid in a yield of 67%.
Further, the following shows the steps by the above steps6 utilization of the yellow solid obtained1Measurement result of H NMR. Further, FIG. 29 shows1H NMR spectrum. From the results, 2Ph-mmnbtBuDPhA2Anth (structural formula (116)) was obtained.
1H NMR(CD2Cl2，300MHz)：σ＝8.39(m，1H)，8.25-8.18(m，3H)，7.65(m，1H)，7.44-7.29(m，7H)，7.05-7.00(m，6H)，6.76-6.63(m，6H)，3.01(m，4H)，2.19(m，8H)，1.78(m，4H)，1.44-0.95(m，64H)。
FIG. 30 shows the results of measurement of the absorption spectrum and emission spectrum of a toluene solution of 2Ph-mmnbtBuDPhA2 Anth. The measurement method was the same as in example 1.
As is clear from FIG. 30, the toluene solution of 2Ph-mmnbtBuDPhA2Anth had an absorption peak near 485nm and an emission peak at 535nm (excitation wavelength of 460 nm).
Example 6
Synthesis example 4
In this example, a method for synthesizing a compound of one embodiment of the present invention represented by the structural formula (108) in embodiment 1, that is, N '-bis [3, 5-bis (1-adamantyl) phenyl ] -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviated as 2 Ph-mmadtudpha 2 anthh-03) will be described. The structure of 2Ph-mmAdtBuDPhA2Anth-03 is shown below.
[ chemical formula 49]
Figure BDA0002659073460001581
The above-mentioned 2Ph-mmAdtBuDPhA2Anth-03 can be synthesized in the same manner as in example 1 by using 3, 5-bis (1-adamantyl) phenyltrifluoromethanesulfonic acid in place of the 3, 5-bis (2-adamantyl) phenyltrifluoromethanesulfonic acid used in step 5 of example 1 and by using the methods shown in the following synthesis scheme (d-1) and synthesis scheme (d-2).
[ chemical formula 50]
Figure BDA0002659073460001591
[ chemical formula 51]
Figure BDA0002659073460001592
Example 7
Synthesis example 5
In this example, a compound of one embodiment of the present invention represented by the structural formula (120) of embodiment 1, i.e., N' -bis {3, 5-bis (tricyclo [5.2.1.0 ]), is described2，6]Decan-8-yl) phenyl } -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviation: 2Ph-mmTCDtBuDPhA2 Anth). The structure of 2Ph-mmTCDtBuDPhA2Anth is shown below.
[ chemical formula 52]
Figure BDA0002659073460001601
<Step 1: 3-bromo-5- (tricyclo [5.2.1.0 ]2，6]Synthesis of decan-8-yl) anisole>
6.7g (25mmol) of 3, 5-dibromoanisole was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 200mL of tetrahydrofuran, and the mixture was stirred at-80 ℃. 17mL (27mmol) of n-butyllithium (1.6mol/L n-hexane solution) was added dropwise to the solution, and the mixture was stirred under a nitrogen stream for 2 hours. Then, 4.3mL (30mmol) of tricyclo [5.2.1.0 ] was added to the mixture2，6]Decan-8-one, stirred for 15 hours while gradually returning the temperature to room temperature.
After stirring, water was added to the mixture, and the aqueous layer was extracted with ethyl acetate. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
The obtained oily substance was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 200mL of methylene chloride, and the mixture was stirred at 0 ℃. To the solution was added 12mL (75mmol) of triethylsilane and 19mL (0.15mmol) of boron trifluoride diethyl ether dropwise, and the mixture was stirred for 15 hours while the temperature was raised to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
This oil was purified by silica gel column chromatography (hexane: toluene: 9: 1 as a developing solvent) to obtain the desired colorless oil. The obtained solid was purified by HPLC (developing solvent: chloroform), whereby 6.6g of the desired product was obtained as a colorless oil in a yield of 81%. The synthetic scheme (e-1) of step 1 is shown below.
[ chemical formula 53]
Figure BDA0002659073460001621
Further, the following shows the utilization of the white solid obtained in the above step 11Measurement result of H NMR. From the results, it was found that 3- (tricyclo [5.2.1.0 ] was obtained2，6]Decan-8-yl) anisole.
1H NMR(CDCl3，300MHz)：σ＝6.95(s，1H)，6.86(m，1H)，6.69(s，1H)，3.78(s，3H)，3.15-3.08(m，1H)，2.17-2.06(m，2H)，1.99-1.52(m，7H)，1.33-1.22(m，2H)，1.14-0.85(m，3H)。
<Step 2: 3, 5-bis (tricyclo [5.2.1.0 ]2，6]Synthesis of decan-8-yl) anisole>
6.6g (20mmol) of 3-bromo-5- (tricyclo [ 5.2.1.0)2，6]Decan-8-yl) anisole was placed in a 500mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 200mL of tetrahydrofuran, and the mixture was stirred at-80 ℃. To the solution, 14mL (22mmol) of n-butyllithium (1.6mol/L n-hexane solution) was added dropwise, and the mixture was stirred under a nitrogen stream for 3 hours. Then, 3.5mL (24mmol) of tricyclo [5.2.1.0 ] was added to the mixture 2，6]Decan-8-one, stirred for 15 hours while gradually returning the temperature to room temperature.
After stirring, water was added to the mixture, and the aqueous layer was extracted with ethyl acetate. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow oil.
The obtained oily substance was placed in a 500mL three-necked flask, and the air in the flask was replaced with nitrogen. To this was added 170mL of methylene chloride and the mixture was stirred at 0 ℃. To the solution was added 9.7mL (61mmol) of triethylsilane and 15mL (0.12mol) of boron trifluoride diethyl ether dropwise, and the mixture was stirred for 15 hours while the temperature was raised to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a pale yellow solid.
This oil was purified by silica gel column chromatography (hexane: toluene ═ 4: 1 as a developing solvent), to give 6.2g of the desired product as a colorless oil. The obtained oil was purified by HPLC (developing solvent: chloroform), whereby 4.0g of the objective colorless oil was obtained in a yield of 52%. The synthetic scheme (e-2) of step 2 is shown below.
[ chemical formula 54]
Figure BDA0002659073460001631
The following shows the use of the colorless oil obtained in step 21Measurement results of HNMR. From the results, it was found that 3, 5-bis (tricyclo [5.2.1.0 ] was obtained2，6]Decan-8-yl) anisole.
1H NMR(CDCl3，300MHz)：σ＝6.69(s，1H)，6.59(s，2H)，3.80(s，3H)，3.19-3.12(m，2H)，2.17-2.06(m，4H)，2.01-1.51(m，14H)，1.40-1.32(m，2H)，1.26-1.23(m，2H)，1.11-0.85(m，6H)。
<And step 3: 3, 5-bis (tricyclo [5.2.1.0 ]2，6]Synthesis of decan-8-yl) phenols>
4.0g (11mmol) of 3, 5-bis (tricyclo [ 5.2.1.0)2，6]Decan-8-yl) anisole was placed in a 300mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 100mL of methylene chloride, and the solution was stirred at 0 ℃. This solution was added dropwise with 22mL of boron tribromide (1.0mol/L dichloromethane solution, 22mmol), and then stirred for 15 hours while the temperature of the solution was raised back to room temperature.
After stirring, the mixture was added dropwise to a saturated aqueous sodium bicarbonate solution, and the aqueous layer of the resulting mixture was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to obtain 4.2g of the objective substance as a gray solid. The synthetic scheme (e-3) of step 3 is shown below.
[ chemical formula 55]
Figure BDA0002659073460001641
Further, the following shows the utilization of the white solid obtained in the above step 3 1Measurement result of H NMR. From the results, it was found that 3, 5-bis (tricyclo [5.2.1.0 ] was obtained2，6]Decan-8-yl) phenol.
1H NMR(CDCl3，300MHz)：σ＝6.67(s，1H)，6.51(s，2H)，4.55(bs，1H)，3.16-3.09(m，2H)，2.16-2.06(m，4H)，2.00-1.51(m，14H)，1.37-1.29(m，2H)，1.25-1.22(m，2H)，1.12-0.85(m，6H)。
<And 4, step 4: 3, 5-bis (tricyclo [5.2.1.0 ]2，6]Synthesis of decan-8-yl) phenyltrifluoromethanesulfonic acid>
4.2g of 3, 5-bis (tricyclo [5.2.1.0 ]2，6]Decan-8-yl) phenol was placed in a 300mL three-necked flask, and the air in the flask was replaced with nitrogenAnd (4) qi. To this was added 100mL of methylene chloride and 5.0mL (36mmol) of triethylamine, and the solution was stirred at 0 ℃. To this was added dropwise a solution of 3.0mL (18mmol) of trifluoromethanesulfonic anhydride in 10mL of dichloromethane, and the mixture was stirred for 15 hours while the temperature was raised back to room temperature.
After stirring, 1N hydrochloric acid was added to the mixture, and the aqueous layer was extracted with dichloromethane. The obtained extract and organic layer were combined, washed with water and saturated brine, and dried over magnesium sulfate. The mixture was separated by gravity filtration, and the filtrate was concentrated to give a brown oil.
This oil was purified by silica gel column chromatography (developing solvent: hexane) to obtain 3.6g of the objective colorless oil in a total yield of 65% (step 3 and step 4). The synthetic scheme (e-4) of step 4 is shown below.
[ chemical formula 56]
Figure BDA0002659073460001661
The following shows the use of the colorless oil obtained in the above step 4 1Measurement results of HNMR. From the results, it was found that 3, 5-bis (tricyclo [5.2.1.0 ] was obtained2，6]Decan-8-yl) phenyltrifluoromethanesulfonic acid.
1H NMR(CDCl3，300MHz)：σ＝7.07(s，1H)，6.90(s，2H)，3.23-3.16(m，2H)，2.19-2.09(m、4H)，2.07-1.97(m，2H)，1.89-1.57(m，12H)，1.34-1.25(m，4H)，1.13-0.86(m，6H)。
<And 5: 3, 5-bis (tricyclo [5.2.1.0 ]2，6]Synthesis of decan-8-yl) -3 ', 5' -di-tert-butyldiphenylamine>
3.6g (7.2mmol) of 3, 5-bis (tricyclo [5.2.1.0 ]2，6]Decan-8-yl) phenyltrifluoromethanesulfonic acid was placed in a 200mL three-necked flask, and the atmosphere in the flask was replaced with nitrogen. To this was added 20mL of tetrahydrofuran, 1.7g (8.3mmol) of 3, 5-di-tert-butylaniline, 3.5g (11mmol) of cesium carbonate and 1.1g (1.7mmol) of (. + -.) -2, 2 '-bis (diphenylphosphino) -1, 1' -binaphthyl (abbreviation)Weighing: (±) -BINAP), the mixture was degassed under reduced pressure, then 0.20g (0.89mmol) of palladium (II) acetate was added to the mixture, and the mixture was stirred at 70 ℃ for 24 hours under a nitrogen stream.
After stirring, 500mL of toluene was added to the resulting mixture, and then a filtrate was obtained by suction filtration using magnesium silicate (Japan and Wako pure chemical industries, Ltd.; catalog number: 066- & 05265), diatomaceous earth (Japan and Wako pure chemical industries, Ltd.; catalog number 537- & 02305), and alumina. The resulting filtrate was concentrated to give a reddish brown solid.
This solid was purified by silica gel column chromatography (developing solvent: hexane: toluene ═ 4: 1), and 3.3g of the desired product was obtained as a white solid in a yield of 83%. The synthetic scheme (e-5) of step 5 is shown below.
[ chemical formula 57]
Figure BDA0002659073460001671
Further, the following shows the utilization of the white solid obtained in the above step 51Measurement result of H NMR. From the results, it was found that 3, 5-bis (tricyclo [5.2.1.0 ] was obtained2，6]Decan-8-yl) -3 ', 5' -di-tert-butyldiphenylamine.
1H NMR(CD2Cl2，300MHz)：σ＝7.00(m，1H)，6.94(m，2H)，6.75(m，2H)，6.66(m，1H)，5.75(bs，1H)，3.17-3.10(m，2H)，2.16-2.05(m，4H)，1.98-1.83(m，8H)，1.75-1.56(m，6H)，1.37-0.87(m，28H)。
< step 6: synthesis of 2Ph-mmTCDtBuDPhA2Anth >
0.41g (0.99mmol) of 9, 10-dibromo-2-phenylanthracene and 1.1g (2.0mmol) of 3, 5-bis (tricyclo [5.2.1.0 ] are added2，6]Decan-8-yl) -3 ', 5 ' -di-tert-butyldiphenylamine, 0.29g (3.0mmol) of sodium tert-butoxide and 80mg (0.19mmol) of 2-dicyclohexylphosphino-2 ', 6 ' -dimethoxy-1, 1 ' -biphenyl (abbreviation: SPhos) was placed in a 200mL three-necked flask, and the air in the flask was replaced with nitrogen. 10mL of xylene was added to the mixture, and the mixture was subjected toThe mixture was degassed under reduced pressure, 60mg (0.10mmol) of bis (dibenzylideneacetone) palladium (0) was added to the mixture, and the mixture was stirred at 150 ℃ for 5 hours under a nitrogen stream.
After stirring, 500mL of toluene was added to the resulting mixture, and then a filtrate was obtained by suction filtration using magnesium silicate (Japan and Wako pure chemical industries, Ltd.; catalog number: 066- & 05265), diatomaceous earth (Japan and Wako pure chemical industries, Ltd.; catalog number 537- & 02305), and alumina. The resulting filtrate was concentrated to give a brown solid.
This solid was purified by silica gel column chromatography (developing solvent: hexane: toluene (concentration ratio) was gradually changed from 9: 1 to 17: 3) to obtain a yellow solid as an objective substance. The obtained yellow solid was recrystallized from ethyl acetate and methanol to obtain 0.17g of the objective yellow solid in a yield of 13%. The synthetic scheme (e-6) of step 6 is shown below.
[ chemical formula 58]
Figure BDA0002659073460001691
0.94g of the yellow solid obtained was purified by sublimation by gradient sublimation. Sublimation purification was carried out by heating the yellow solid at 305 ℃ for 15 hours under a pressure of 5.7 Pa. After purification by sublimation, 0.79g of the objective substance was obtained as a yellow solid in a recovery rate of 84%.
Further, the following shows the utilization of the yellow solid obtained in the above step 61Measurement result of H NMR. Further, FIG. 31 shows1H NMR spectrum. From the results, 2Ph-mmTCDtBuDPhA2Anth (structural formula (120)) was obtained.
1H NMR(CD2Cl2，300MHz)：σ＝8.40-8.39(m，1H)，8.25-8.16(m，3H)，7.67-7.61(m，1H)，7.43-7.27(m，7H)，7.09-7.01(m，6H)，6.79-6.63(m，6H)，3.00(m，4H)，1.95-1.43(m，36H)，1.18-0.82(m，56H)。
FIG. 32 shows the results of measurement of the absorption spectrum and emission spectrum of a toluene solution of 2Ph-mmTCDtBuDPhA2 Anth. The measurement method was the same as in example 1.
As is clear from FIG. 32, the toluene solution of 2Ph-mmTCDtBuDPhA2Anth had an absorption peak at around 488nm and an emission wavelength peak of 537nm (excitation wavelength of 460 nm).
Example 8
In this example, a light-emitting device was manufactured using the compound of one embodiment of the present invention and operating characteristics were measured. The light emitting devices shown in this embodiment are the light emitting device 3-1, the light emitting device 3-2, the light emitting device 3-3, the light emitting device 3-4, and the light emitting device 3-5. These light-emitting devices have the device structure shown in fig. 16 and the structure described in < structure example 5> of light-emitting layer of embodiment mode 2, specifically, the structure shown in table 5. These light-emitting devices have only a content of the compound of one embodiment of the present invention, that is, N '-bis [3, 5-bis (2-adamantyl) phenyl ] -N, N' -bis [3, 5-bis (3, 5-di-tert-butylphenyl) phenyl ] -2-phenylanthracene-9, 10-diamine (abbreviated as 2 Ph-mmadtbudpa a2 nth-02 (structural formula (102)) contained in a light-emitting layer of the light-emitting device, but the other structures are the same.
[ Table 5]
Figure BDA0002659073460001711
* mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmAdtBuDPhA2Anth-02(0.5∶0.5∶0.1∶0.01 40nm)
** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmAdtBuDPhA2Anth-02(0.5∶0.5∶0.1∶0.025 40nm)
*** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmAdtBuDPhA2Anth-02(0.5∶0.5∶0.1∶0.05 40nm)
**** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmAdtBuDPhA2Anth-02(0.5∶0.5∶0.1∶0.1 40nm)
***** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)](0.5∶0.5∶0.1 40nm)
[ chemical formula 59]
Figure BDA0002659073460001721
Structure of light emitting device
The light-emitting device shown in this embodiment has a structure shown in fig. 16, as in embodiment 2. The structure of the light emitting device shown in this embodiment is different from that of embodiment 2 in that: in the light-emitting device 3-1, the light-emitting device 3-2, the light-emitting device 3-3, and the light-emitting device 3-4, 2 Ph-mmadbus dpha2 nth-02 is used for the light-emitting layer 913.
Operating characteristics of light-emitting device
The operating characteristics of the fabricated light emitting device were tested. For measurement of luminance, chromaticity (CIE chromaticity) and Electroluminescence (EL) spectrum, a spectral radiance luminance meter (SR-UL 1R manufactured by Topcon Technohouse corporation) was used. Note that the measurement was performed at room temperature (atmosphere maintained at 23 ℃).
As the measurement results of the operation characteristics of the light emitting devices 3-1 to 3-5 manufactured in the present embodiment, fig. 35 to 39 respectively show a current density-luminance characteristic, a voltage-luminance characteristic, a luminance-current efficiency characteristic, a voltage-current density characteristic, and a luminance-external quantum efficiency characteristic.
FIG. 40 shows the signal at 2.5mA/cm2The current density of (a) is an electroluminescence spectrum (EL spectrum) when a current flows through each light emitting device.
Table 6 shows 1000cd/m2Main initial characteristic values of the respective light emitting devices in the vicinity.
[ Table 6]
Figure BDA0002659073460001731
The light-emitting devices 3-1 to 3-4 are devices in which a compound according to one embodiment of the present invention, i.e., 2 Ph-mmadtudpha 2 ath-02 is added to the light-emitting device 3-5. As shown in FIG. 40, the EL spectra of the light-emitting devices 3 to 5 showed a peak wavelength of 522nm derived from [ Ir (ppy)2(mdppy)]The green color of (2) emits light. Further, the light emitting device 3-1 emits lightThe EL spectrum of the optical device 3-4 showed green emission originating from 2Ph-mmAdtBuDPhA2Anth-02 with a peak wavelength of about 540 nm. From this, it is known that in the light-emitting devices 3-1 to 3-4, 2Ph-mmAdtBuDPhA2Anth-02 as a fluorescent light-emitting substance receives excitation energy to emit light. In addition, the above results indicate that the external quantum efficiencies of the light emitting devices 3-1 to 3-5 are all as high as 18% or more. Here, since the maximum generation probability of the singlet excitons generated by the recombination of the carriers (holes and electrons) injected from the pair of electrodes is 25%, the maximum external quantum efficiency of the fluorescent light-emitting device is 7.5% when the light extraction efficiency to the outside is 30%. However, external quantum efficiencies of more than 7.5% were obtained in the light emitting devices 3-1 to 3-4. This is because: the fluorescent substance can emit light from singlet excitons generated by recombination of carriers (holes and electrons) injected from a pair of electrodes, and also from energy transfer of triplet excitons.
It can also be known that: in comparison between the light-emitting devices 3-1 to 3-5 in which the concentrations of 2Ph-mmAdtBuDPhA2Anth-02 included in the light-emitting layer were different, the light-emitting devices 3-1 to 3-5 all had equivalent external quantum efficiencies. Thus, the compound according to one embodiment of the present invention, i.e., 2 Ph-mmadtudpha 2 ath-02 can suppress deactivation of triplet excitation energy which is particularly significant when the light-emitting layer of the light-emitting device has a high concentration, and thus can emit light with high efficiency.
Example 9
In this example, a light-emitting device was manufactured using the compound of one embodiment of the present invention and operating characteristics were measured. The light emitting devices shown in this embodiment are the light emitting device 4-1, the light emitting device 4-2, the light emitting device 4-3, the light emitting device 4-4, and the light emitting device 4-5. These light-emitting devices have the device structure shown in fig. 16 and the structure described in < structure example 3> of light-emitting layer of embodiment mode 2, specifically, the structure shown in table 7. These light-emitting devices have only a content of the compound of one embodiment of the present invention, that is, N '-bis [3, 5-bis (2-adamantyl) phenyl ] -N, N' -bis [3, 5-bis (3, 5-di-tert-butylphenyl) phenyl ] -2-phenylanthracene-9, 10-diamine (abbreviated as 2 Ph-mmadtbudpa a2 nth-02 (structural formula (102)) contained in a light-emitting layer of the light-emitting device, but the other structures are the same.
[ Table 7]
Figure BDA0002659073460001751
* 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmAdtBuDPhA2Anth-02(0.8∶0.2∶0.01 40nm)
** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmAdtBuDPhA2Anth-02(0.8∶0.2∶0.025 40nm)
*** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmAdtBuDPhA2Anth-02(0.8∶0.2∶0.05 40nm)
**** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmAdtBuDPhA2Anth-02(0.8∶0.2∶0.1 40nm)
***** 4，6mCzP2Pm∶[Ir(ppz)3](0.8∶0.2 40nm)
[ chemical formula 60]
Figure BDA0002659073460001761
Structure of light emitting device
The light-emitting device shown in this embodiment has a structure shown in fig. 16, as in embodiment 8. The structure of the light emitting device shown in this embodiment is different from that of embodiment 8 in that: in the light-emitting device 4-1, the light-emitting device 4-2, the light-emitting device 4-3, the light-emitting device 4-4, and the light-emitting device 4-5, 3' -bis (9-phenyl-9H-carbazole) (abbreviated as PCCP) is used for the hole-transporting layer 912, and tris [2- (1H-pyrazol-1-yl- κ N2) phenyl- κ C is used for the light-emitting layer 913]Iridium (III) (abbreviation: [ Ir (ppz))3]) And 9, 9' - (pyrimidine-4, 6-diylbis-3, 1-phenylene) bis (9H-carbazole) (abbreviation: 4, 6mCzP2Pm), and electron transport layer 914 used 4, 6mCzP2 Pm.
Operating characteristics of light-emitting device
The operating characteristics of the fabricated light emitting device were tested. The test method is the same as in example 8, and thus the description is omitted.
As the measurement results of the operation characteristics of the light emitting devices 4-1 to 4-5 manufactured in the present embodiment, fig. 41 to 45 respectively show a current density-luminance characteristic, a voltage-luminance characteristic, a luminance-current efficiency characteristic, a voltage-current density characteristic, and a luminance-external quantum efficiency characteristic.
FIG. 46 shows the signal at 2.5mA/cm 2The current density of (a) is an electroluminescence spectrum (EL spectrum) when a current flows through each light emitting device.
Table 8 shows 1000cd/m2Main initial characteristic values of the respective light emitting devices in the vicinity.
[ Table 8]
Figure BDA0002659073460001771
The light-emitting devices 4-1 to 4 are devices in which a compound which is one embodiment of the present invention, i.e., 2 Ph-mmadbus dpha2 nth-02 is added to the light-emitting device 4-5. As shown in FIG. 46, the EL spectrum of each of the light-emitting devices 4 to 5 showed peaks at 531nm derived from 4, 6mCZP2Pm and [ Ir (ppz) ]3]Does not originate from 4, 6mCZP2Pm and [ Ir (ppz)3]Green luminescence of the emission spectra respectively present. Further, the EL spectra of the light-emitting devices 4-1 to 4-4 showed green luminescence derived from 2Ph-mmAdtBuDPhA2Anth-02 with a peak wavelength of about 540 nm. From this, it is known that in the light-emitting devices 4-1 to 4-4, 2Ph-mmAdtBuDPhA2Anth-02 as a fluorescent light-emitting substance receives excitation energy to emit light. In addition, the above results indicate that the external quantum efficiencies of the light emitting devices 4-1 to 4-5 are all as high as 19% or more. Here, since the maximum generation probability of the singlet excitons generated by the recombination of the carriers (holes and electrons) injected from the pair of electrodes is 25%, the maximum external quantum efficiency of the fluorescent light-emitting device is 7.5% when the light extraction efficiency to the outside is 30%. However, external quantum efficiencies of more than 7.5% were obtained in the light emitting devices 4-1 to 4. This is because: the fluorescent substance is generated by recombination of carriers (holes and electrons) injected from a pair of electrodes In addition to the emission of singlet excitons (a), emission derived from energy transfer of triplet excitons or emission derived from singlet excitons generated from triplet excitons by intersystem crossing in an exciplex is obtained.
It can also be known that: in comparison between the light-emitting devices 4-1 to 4-5 in which the concentrations of 2Ph-mmAdtBuDPhA2Anth-02 included in the light-emitting layer were different, the light-emitting devices 4-1 to 4-5 all had equivalent external quantum efficiencies. Thus, the compound according to one embodiment of the present invention, i.e., 2 Ph-mmadtudpha 2 ath-02 can suppress deactivation of triplet excitation energy which is particularly significant when the light-emitting layer of the light-emitting device has a high concentration, and thus can emit light with high efficiency.
Further, 50mA/cm was applied to each of the light emitting devices 4-1 to 4-52A constant current density drive test was performed. Fig. 47 shows the result thereof. From these results, it is understood that the reliability is improved when the concentration of guest 2Ph-mmAdtBuDPhA2Anth-02 is increased. This means that: when the guest concentration in the light-emitting layer is increased, the excitation energy in the light-emitting layer can be efficiently converted into light emission of the guest. That is, in the case of increasing the concentration of the guest, the energy transfer rate of triplet excitation energy based on the forster mechanism from the host to the guest can be increased while suppressing the energy transfer based on the dexter mechanism from the host to the guest. Therefore, a light-emitting device using the compound of one embodiment of the present invention has good light-emitting efficiency and reliability.
Example 10
In this example, a light-emitting device was manufactured using the compound of one embodiment of the present invention and operating characteristics were measured. The light emitting devices shown in this embodiment are the light emitting device 5-1, the light emitting device 5-2, the light emitting device 5-3, the light emitting device 5-4, and the light emitting device 5-5. These light-emitting devices have the device structure shown in fig. 16 and the structure described in < structure example 5> of light-emitting layer of embodiment mode 2, specifically, the structure shown in table 9. These light-emitting devices have only a content of the compound according to one embodiment of the present invention, i.e., N '-bis {3, 5-bis (2-bicyclo [2.2.1] heptyl) phenyl } -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviated as: 2 Ph-mmnbtbutbha 2 anthh) (structural formula (116)), contained in a light-emitting layer of the light-emitting device, but the other structures are the same. The chemical formula of the material used in this example is shown below.
[ Table 9]
Figure BDA0002659073460001801
* mPCCzPTzn-02∶PCCP∶[Ir(PPy)2(mdppy)]∶2Ph-mmnbtBuDPhA2Anth(0.5∶0.5∶0.1∶0.01 40nm)
** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmnbtBuDPhA2Anth(0.5∶0.5∶0.1∶0.025 40nm)
*** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmnbtBuDPhA2Anth(0.5∶0.5∶0.1∶0.05 40nm)
**** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmnbtBuDPhA2Anth(0.5∶0.5∶0.1∶0.1 40nm)
***** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)](0.5∶0.5∶0.1 40nm)
[ chemical formula 61]
Figure BDA0002659073460001811
Structure of light emitting device
The light-emitting device shown in this embodiment has a structure shown in fig. 16, as in embodiment 2. The structure of the light emitting device shown in this embodiment is different from that of embodiment 2 in that: in the light-emitting device 5-1, the light-emitting device 5-2, the light-emitting device 5-3, and the light-emitting device 5-4, 2Ph-mmnbtbudph Ph a2 ath is used for the light-emitting layer 913.
Operating characteristics of light-emitting device
The operating characteristics of the fabricated light emitting device were tested. For measurement of luminance, chromaticity (CIE chromaticity) and Electroluminescence (EL) spectrum, a spectral radiance luminance meter (SR-UL 1R manufactured by Topcon Technohouse corporation) was used. Note that the measurement was performed at room temperature (atmosphere maintained at 23 ℃).
As the measurement results of the operation characteristics of the light emitting devices 5-1 to 5 made in the present embodiment, fig. 48 to 52 respectively show a current density-luminance characteristic, a voltage-luminance characteristic, a luminance-current efficiency characteristic, a voltage-current density characteristic, and a luminance-external quantum efficiency characteristic.
FIG. 53 shows a signal at 2.5mA/cm2The current density of (a) is an electroluminescence spectrum (EL spectrum) when a current flows through each light emitting device.
Table 10 shows 1000cd/m2Main initial characteristic values of the respective light emitting devices in the vicinity.
[ Table 10]
Figure BDA0002659073460001821
The light-emitting devices 5-1 to 5-4 are devices in which a compound which is one embodiment of the present invention, i.e., 2Ph-mmnbtbudph a2 ath, is added to the light-emitting device 5-5. As shown in FIG. 53, the EL spectrum of the light-emitting device 5-5 showed a peak wavelength of 522nm derived from [ Ir (ppy)2(mdppy)]The green color of (2) emits light. Further, the EL spectra of the light-emitting devices 5-1 to 5-4 showed green luminescence derived from 2Ph-mmnbtBuDPhA2Anth with a peak wavelength of about 540 nm. From this, it is known that in the light-emitting devices 5-1 to 5-4, 2Ph-mmnbtBuDPhA2Anth as a fluorescent light-emitting substance receives excitation energy to emit light. In addition, the above results indicate that the external quantum efficiencies of the light emitting device 5-1 to the light emitting device 5-5 are all as high as 16% or more. Here, since the maximum generation probability of the singlet excitons generated by the recombination of the carriers (holes and electrons) injected from the pair of electrodes is 25%, the maximum external quantum efficiency of the fluorescent light-emitting device is 7.5% when the light extraction efficiency to the outside is 30%. However, external quantum efficiencies of more than 7.5% were obtained in the light emitting devices 5-1 to 5-4. This is because: the fluorescent substance can emit light from singlet excitons generated by recombination of carriers (holes and electrons) injected from a pair of electrodes, and also from energy transfer of triplet excitons.
It can also be known that: in comparison between the light-emitting devices 5-1 to 5 in which the concentrations of 2Ph-mmnbtBuDPhA2Anth contained in the light-emitting layer were different, the light-emitting devices 5-1 to 5 all had equivalent external quantum efficiencies. Thus, the compound according to one embodiment of the present invention, i.e., 2Ph-mmnbtbudph Ph ha2Anth can suppress deactivation of triplet excitation energy which is particularly significant when the light-emitting layer of the light-emitting device has a high concentration, and thus can emit light with high efficiency.
Example 11
In this example, a light-emitting device was manufactured using the compound of one embodiment of the present invention and operating characteristics were measured. The light emitting devices shown in this embodiment are the light emitting device 6-1, the light emitting device 6-2, the light emitting device 6-3, the light emitting device 6-4, and the light emitting device 6-5. These light-emitting devices have the device structure shown in fig. 16 and the structure described in < structure example 3> of light-emitting layer of embodiment mode 2, specifically, the structure shown in table 11. These light-emitting devices include only the compound according to one embodiment of the present invention, that is, N '-bis [3, 5-bis { 2-bicyclo [2.2.1] heptyl) phenyl } -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviation: the content of 2Ph-mmnbtBuDPhA2Anth (structural formula (116)) was varied, but the other structures were the same. The chemical formula of the material used in this example is shown below.
[ Table 11]
Figure BDA0002659073460001841
* 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmnbtBuDPhA2Anth(0.8∶0.2∶0.01 40nm)
** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmnbtBuDPhA2Anth(0.8∶0.2∶0.025 40nm)
*** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmnbtBuDPhA2Anth(0.8∶0.2∶0.05 40nm)
**** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmnbtBuDPhA2Anth(0.8∶0.2∶0.1 40nm)
***** 4，6mCzP2Pm∶[Ir(ppz)3](0.8∶0.2 40nm)
[ chemical formula 62]
Figure BDA0002659073460001851
Structure of light emitting device
The light-emitting device shown in this embodiment has a structure shown in fig. 16, as in embodiment 10. The structure of the light emitting device shown in this embodiment is different from that of embodiment 10 in that: in the light-emitting device 6-1, the light-emitting device 6-2, the light-emitting device 6-3, the light-emitting device 6-4, and the light-emitting device 6-5, 3' -bis (9-phenyl-9H-carbazole) (abbreviated as PCCP) is used for the hole-transporting layer 912, and tris [2- (1H-pyrazol-1-yl- κ N2) phenyl- κ C is used for the light-emitting layer 913]Iridium (III) (abbreviation: [ Ir (ppz))3]) And 9, 9' - (pyrimidine-4, 6-diylbis-3, 1-phenylene) bis (9H-carbazole) (abbreviation: 4, 6mCzP2Pm), and electron transport layer 914 used 4, 6mCzP2 Pm.
Operating characteristics of light-emitting device
The operating characteristics of the fabricated light emitting device were tested. The test method is the same as in example 10, and thus, the description thereof is omitted.
As the measurement results of the operation characteristics of the light emitting devices 6-1 to 6-5 manufactured in the present embodiment, fig. 54 to 58 respectively show a current density-luminance characteristic, a voltage-luminance characteristic, a luminance-current efficiency characteristic, a voltage-current density characteristic, and a luminance-external quantum efficiency characteristic.
FIG. 59 shows the signal at 2.5mA/cm 2The current density of (a) is an electroluminescence spectrum (EL spectrum) when a current flows through each light emitting device.
Table 12 shows 1000cd/m2Main initial characteristic values of the respective light emitting devices in the vicinity.
[ Table 12]
Figure BDA0002659073460001861
The light emitting devices 6-1 to 6-4 are one in which the present invention is added to the light emitting device 6-5Compound of mode (i.e., device of 2Ph-mmnbtBuDPhA2 Anth). As shown in FIG. 59, the EL spectrum of the light-emitting device 6-5 showed peaks at 531nm derived from 4, 6mCZP2Pm and [ Ir (ppz) ]3]Does not originate from 4, 6mCZP2Pm and [ Ir (ppz)3]Green luminescence of the emission spectra respectively present. Further, the EL spectra of the light-emitting devices 6-1 to 6-4 showed green luminescence derived from 2Ph-mmnbtBuDPhA2Anth with a peak wavelength of about 540 nm. From this, it is known that in the light-emitting devices 6-1 to 6-4, 2Ph-mmnbtBuDPhA2Anth as a fluorescent light-emitting substance receives excitation energy to emit light. In addition, the above results indicate that the external quantum efficiencies of the light emitting devices 6-1 to 6-5 are all as high as 19% or more. Here, since the maximum generation probability of the singlet excitons generated by the recombination of the carriers (holes and electrons) injected from the pair of electrodes is 25%, the maximum external quantum efficiency of the fluorescent light-emitting device is 7.5% when the light extraction efficiency to the outside is 30%. However, external quantum efficiencies of more than 7.5% were obtained in the light emitting devices 6-1 to 6-4. This is because: the fluorescent light-emitting substance can emit light from singlet excitons generated by recombination of carriers (holes and electrons) injected from a pair of electrodes, and also can emit light from energy transfer of triplet excitons or light from singlet excitons generated from triplet excitons through intersystem crossing in an exciplex.
It can also be known that: in comparison between the light-emitting devices 6-1 to 6-5 in which the concentrations of 2Ph-mmnbtBuDPhA2Anth contained in the light-emitting layer were different, the light-emitting devices 6-1 to 6-5 all had equivalent external quantum efficiencies. Thus, the compound according to one embodiment of the present invention, i.e., 2Ph-mmnbtbudph Ph ha2Anth can suppress deactivation of triplet excitation energy which is particularly significant when the light-emitting layer of the light-emitting device has a high concentration, and thus can emit light with high efficiency.
Further, 50mA/cm was applied to the light emitting devices 6-1 to 6-52A constant current density drive test was performed. Fig. 60 shows the results. From the results, it is understood that the reliability is improved when the concentration of guest 2Ph-mmnbtBuDPhA2Anth is increased. This means that: when the guest concentration in the light-emitting layer is increased, the concentration of the guest in the light-emitting layer can be increasedThe excitation energy in the light-emitting layer is efficiently converted into light emission of the guest. That is, in the case of increasing the concentration of the guest, the energy transfer rate of triplet excitation energy based on the forster mechanism from the host to the guest can be increased while suppressing the energy transfer based on the dexter mechanism from the host to the guest. Therefore, a light-emitting device using the compound of one embodiment of the present invention has good light-emitting efficiency and reliability.
Example 12
In this example, a light-emitting device was manufactured using the compound of one embodiment of the present invention and operating characteristics were measured. The light emitting devices shown in this embodiment are the light emitting device 7-1, the light emitting device 7-2, the light emitting device 7-3, the light emitting device 7-4, and the light emitting device 7-5. These light-emitting devices have the device structure shown in fig. 16 and those of embodiment 2<Structure example 5 of light emitting layer>Specifically, the above-described structure has the structure shown in table 13. These light-emitting devices have only the compound of one embodiment of the present invention, i.e., N' -bis {3, 5-bis (tricyclo [5.2.1.0 ]), contained in the light-emitting layer of the light-emitting device2，6]Decan-8-yl) phenyl } -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviation: the content of 2Ph-mmTCDtBuDPhA2Anth (structural formula (120)) was varied, but the other structures were the same. The chemical formula of the material used in this example is shown below.
[ Table 13]
Figure BDA0002659073460001891
* mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmTCDtBuDPhA2Anth(0.5∶0.5∶0.1∶0.01 40nm)
** mPCCzPTzn-02∶PCCP∶[Ir(PPy)2(mdppy)]∶2Ph-mmTCDtBuDPhA2Anth(0.5∶0.5∶0.1∶0.025 40nm)
*** mPCCzPTzn-02∶PCCP∶[Ir(PPy)2(mdppy)]∶2Ph-mmTCDtBuDPhA2Anth(0.5∶0.5∶0.1∶0.05 40nm)
**** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)]∶2Ph-mmTCDtBuDPhA2Anth(0.5∶0.5∶0.1∶0.1 40nm)
***** mPCCzPTzn-02∶PCCP∶[Ir(ppy)2(mdppy)](0.5∶0.5∶0.1 40nm)
[ chemical formula 63]
Figure BDA0002659073460001901
Structure of light emitting device
The light-emitting device shown in this embodiment has a structure shown in fig. 16, as in embodiment 10. The structure of the light emitting device shown in this embodiment is different from that of embodiment 10 in that: in the light-emitting device 7-1, the light-emitting device 7-2, the light-emitting device 7-3, and the light-emitting device 7-4, 2 Ph-mmtcdtbhpa 2 ath is used for the light-emitting layer 913.
Operating characteristics of light-emitting device
The operating characteristics of the fabricated light emitting device were tested. For measurement of luminance, chromaticity (CIE chromaticity) and Electroluminescence (EL) spectrum, a spectral radiance luminance meter (SR-UL 1R manufactured by Topcon Technohouse corporation) was used. Note that the measurement was performed at room temperature (atmosphere maintained at 23 ℃).
As the measurement results of the operation characteristics of the light emitting devices 7-1 to 7-5 manufactured in the present embodiment, fig. 61 to 65 respectively show a current density-luminance characteristic, a voltage-luminance characteristic, a luminance-current efficiency characteristic, a voltage-current density characteristic, and a luminance-external quantum efficiency characteristic.
FIG. 66 shows a signal at 2.5mA/cm2The current density of (a) is an electroluminescence spectrum (EL spectrum) when a current flows through each light emitting device.
Table 14 shows 1000cd/m2Main initial characteristic values of the respective light emitting devices in the vicinity.
[ Table 14]
Figure BDA0002659073460001921
The light emitting devices 7-1 to 7-4 are ones to which the present invention is added to the light emitting device 7-5A compound of one mode, namely 2Ph-mmTCDtBuDPhA2 Anth. As shown in FIG. 66, the EL spectrum of the light-emitting device 7-5 showed a peak wavelength of 522nm derived from [ Ir (PPy) ]2(mdppy)]The green color of (2) emits light. Further, the EL spectra of the light-emitting devices 7-1 to 7-4 showed green luminescence derived from 2Ph-mmTCDtBuDPhA2Anth with a peak wavelength of about 540 nm. From this, it is known that in the light-emitting devices 7-1 to 7-4, 2Ph-mmTCDtBuDPhA2Anth as a fluorescent light-emitting substance receives excitation energy to emit light. In addition, the above results indicate that the external quantum efficiencies of the light emitting devices 7-1 to 7-5 are all as high as 18% or more. Here, since the maximum generation probability of the singlet excitons generated by the recombination of the carriers (holes and electrons) injected from the pair of electrodes is 25%, the maximum external quantum efficiency of the fluorescent light-emitting device is 7.5% when the light extraction efficiency to the outside is 30%. However, external quantum efficiencies of more than 7.5% were obtained in the light emitting devices 7-1 to 7-4. This is because: the fluorescent substance can emit light from singlet excitons generated by recombination of carriers (holes and electrons) injected from a pair of electrodes, and also from energy transfer of triplet excitons.
It can also be known that: in comparison between the light emitting devices 7-1 to 7-5 in which the concentrations of 2Ph-mmTCDtBuDPhA2Anth contained in the light emitting layers were different, the light emitting devices 7-1 to 7-5 all had equivalent external quantum efficiencies. Thus, the compound according to one embodiment of the present invention, i.e., 2 Ph-mmtcdtbhdpha 2 ath, can suppress deactivation of triplet excitation energy which is particularly significant when the light-emitting layer of the light-emitting device has a high concentration, and thus can emit light with high efficiency.
Further, 50mA/cm was applied to each of the light emitting devices 7-1 to 7-52A constant current density drive test was performed. Fig. 67 shows the results. From the results, it is understood that the reliability is improved when the concentration of guest 2Ph-mmTCDtBuDPhA2Anth is increased. This means that: when the guest concentration in the light-emitting layer is increased, the excitation energy in the light-emitting layer can be efficiently converted into light emission of the guest. That is, in the case of increasing the concentration of the guest, energy transfer based on the dexter mechanism from the host to the guest can be suppressed while suppressingIncreasing the energy transfer rate of triplet excitation energy based on the Forster mechanism from host to guest. Therefore, a light-emitting device using the compound of one embodiment of the present invention has good light-emitting efficiency and reliability.
Example 13
In this example, a light-emitting device was manufactured using the compound of one embodiment of the present invention and operating characteristics were measured. The light emitting devices shown in this embodiment are the light emitting device 8-1, the light emitting device 8-2, the light emitting device 8-3, the light emitting device 8-4, and the light emitting device 8-5. These light-emitting devices have the device structure shown in fig. 16 and those of embodiment 2<Structure example 3 of light emitting layer>Specifically, the above-described structure has the structure shown in table 15. These light-emitting devices have only the compound of one embodiment of the present invention, i.e., N' -bis {3, 5-bis (tricyclo [5.2.1.0 ]), contained in the light-emitting layer of the light-emitting device2，6]Decan-8-yl) phenyl } -N, N' -bis (3, 5-di-tert-butylphenyl) -2-phenylanthracene-9, 10-diamine (abbreviation: the content of 2Ph-mmTCDtBuDPhA2Anth (structural formula (120)) was varied, but the other structures were the same. The chemical formula of the material used in this example is shown below.
[ Table 15]
Figure BDA0002659073460001941
* 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmTCDtBuDPhA2Anth(0.8∶0.2∶0.01 40nm)
** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmTCDtBuDPhA2Anth(0.8∶0.2∶0.025 40nm)
*** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmTCDtBuDPhA2Anth(0.8∶0.2∶0.05 40nm)
**** 4，6mCzP2Pm∶[Ir(ppz)3]∶2Ph-mmTCDtBuDPhA2Anth(0.8∶0.2∶0.1 40nm)
***** 4，6mCzP2Pm∶[Ir(ppz)3](0.8∶0.2 40nm)
[ chemical formula 64]
Figure BDA0002659073460001951
Structure of light emitting device
The light-emitting device shown in this example has a structure shown in fig. 16, as in example 12. The structure of the light emitting device shown in this embodiment is different from that of embodiment 12 in that: in the light-emitting device 8-1, the light-emitting device 8-2, the light-emitting device 8-3, the light-emitting device 8-4, and the light-emitting device 8-5, 3' -bis (9-phenyl-9H-carbazole) (abbreviated as PCCP) is used for the hole-transporting layer 912, and tris [2- (1H-pyrazol-1-yl- κ N2) phenyl- κ C is used for the light-emitting layer 913 ]Iridium (III) (abbreviation: [ Ir (ppz))3]) And 9, 9' - (pyrimidine-4, 6-diylbis-3, 1-phenylene) bis (9H-carbazole) (abbreviation: 4, 6mCzP2Pm), and electron transport layer 914 used 4, 6mCzP2 Pm.
Operating characteristics of light-emitting device
The operating characteristics of the fabricated light emitting device were tested. The test method is the same as in example 12, and thus, the description thereof is omitted.
As the measurement results of the operation characteristics of the light emitting devices 8-1 to 8-5 manufactured in the present embodiment, fig. 68 to 72 respectively show a current density-luminance characteristic, a voltage-luminance characteristic, a luminance-current efficiency characteristic, a voltage-current density characteristic, and a luminance-external quantum efficiency characteristic.
FIG. 73 shows the signal at 2.5mA/cm2The current density of (a) is an electroluminescence spectrum (EL spectrum) when a current flows through each light emitting device.
Table 16 shows 1000cd/m2Main initial characteristic values of the respective light emitting devices in the vicinity.
[ Table 16]
Figure BDA0002659073460001961
The light-emitting devices 8-1 to 8-4 are devices in which a compound which is one embodiment of the present invention, i.e., 2 Ph-mmtcdtbhpa 2 ath, is added to the light-emitting device 8-5. As shown in FIG. 73, the EL spectrum of the light-emitting device 8-5 showed peaks at 531nm derived from 4, 6mCzP2Pm and [ Ir (pp) ]z)3]Does not originate from 4, 6mCZP2Pm and [ Ir (ppz) 3]Green luminescence of the emission spectra respectively present. Further, the EL spectra of the light-emitting devices 8-1 to 8-4 showed green luminescence derived from 2Ph-mmTCDtBuDPhA2Anth with a peak wavelength of about 540 nm. From this, it is known that in the light-emitting devices 8-1 to 8-4, 2Ph-mmTCDtBuDPhA2Anth as a fluorescent light-emitting substance receives excitation energy to emit light. In addition, the above results indicate that the external quantum efficiencies of the light emitting devices 8-1 to 8-5 are all as high as 19% or more. Here, since the maximum generation probability of the singlet excitons generated by the recombination of the carriers (holes and electrons) injected from the pair of electrodes is 25%, the maximum external quantum efficiency of the fluorescent light-emitting device is 7.5% when the light extraction efficiency to the outside is 30%. However, external quantum efficiencies of more than 7.5% were obtained in the light emitting devices 8-1 to 8-4. This is because: the fluorescent light-emitting substance can emit light from singlet excitons generated by recombination of carriers (holes and electrons) injected from a pair of electrodes, and also can emit light from energy transfer of triplet excitons or light from singlet excitons generated from triplet excitons through intersystem crossing in an exciplex.
It can also be known that: in comparison between the light-emitting devices 8-1 to 8-5 in which the concentrations of 2Ph-mmTCDtBuDPhA2Anth contained in the light-emitting layers were different, the light-emitting devices 8-1 to 8-5 all had equivalent external quantum efficiencies. Thus, the compound according to one embodiment of the present invention, i.e., 2 Ph-mmtcdtbhdpha 2 ath, can suppress deactivation of triplet excitation energy which is particularly significant when the light-emitting layer of the light-emitting device has a high concentration, and thus can emit light with high efficiency.
Further, 50mA/cm was applied to each of the light-emitting devices 8-1 to 8-52A constant current density drive test was performed. Fig. 74 shows the result thereof. From the results, it is understood that the reliability is improved when the concentration of guest 2Ph-mmTCDtBuDPhA2Anth is increased. This means that: when the guest concentration in the light-emitting layer is increased, the excitation energy in the light-emitting layer can be efficiently converted into light emission of the guest. That is, in the case of increasing the concentration of the guest, the concentration of the guest can be suppressed from the host to the guestThe energy transfer based on the dexter mechanism is simultaneously increased in the energy transfer speed of the triplet excitation energy based on the forster mechanism from the host to the guest. Therefore, a light-emitting device using the compound of one embodiment of the present invention has good light-emitting efficiency and reliability.
Description of the symbols
101: first electrode, 102: second electrode, 103: EL layer, 103a, 103 b: EL layer, 104: charge generation layer, 111a, 111 b: hole injection layer, 112a, 112 b: hole transport layer, 113a, 113 b: light-emitting layers, 114a, 114 b: electron transport layer, 115a, 115 b: electron injection layer, 121: first organic compound, 122: second organic compound, 123: third organic compound, 124: fluorescent substance, 130a, 130 b: illuminant, 131: protecting groups, 200R, 200G, 200B: optical distance, 201: first substrate, 202: transistor (FET), 203R, 203G, 203B, 203W: light-emitting device, 204: EL layer, 205: second substrate, 206R, 206G, 206B: color filters, 206R ', 206G ', 206B ': color filter, 207: first electrode, 208: second electrode, 209: black layer (black matrix), 210R, 210G: conductive layer, 301: first substrate, 302: pixel portion, 303: driver circuit portion (source line driver circuit), 304a, 304 b: driver circuit portion (gate line driver circuit), 305: sealant, 306: second substrate, 307: lead, 308: FPC, 309: FET, 310: FET, 311: FET, 312: FET, 313: first electrode, 314: insulator, 315: EL layer, 316: second electrode, 317: light emitting device, 318: space, 900: substrate, 901: first electrode, 902: EL layer, 903: second electrode, 911: hole injection layer, 912: hole-transport layer, 913: light-emitting layer, 914: electron transport layer, 915: electron injection layer, 4000: lighting device, 4001: substrate, 4002: light-emitting device, 4003: substrate, 4004: first electrode, 4005: EL layer, 4006: second electrode, 4007: electrode, 4008: electrode, 4009: auxiliary wiring, 4010: insulating layer, 4011: sealing substrate, 4012: sealant, 4013: drying agent, 4200: lighting device, 4201: substrate, 4202: light-emitting device, 4204: first electrode, 4205: EL layer, 4206: second electrode, 4207: electrode, 4208: electrode, 4209: auxiliary wiring, 4210: insulating layer, 4211: sealing substrate, 4212: sealant, 4213: barrier film, 4214: planarizing film, 5101: lamp, 5102: hub, 5103: vehicle door, 5104: display unit, 5105: steering wheel, 5106: gear lever, 5107: seat, 5108: interior rearview mirror, 5109: windshield, 7000: case, 7001: display unit, 7002: second display portion, 7003: speaker, 7004: LED lamp, 7005: operation keys, 7006: connection terminal, 7007: sensor, 7008: microphone, 7009: switch, 7010: infrared port, 7011: recording medium reading unit, 7014: antenna, 7015: shutter button, 7016: image receiving unit, 7018: stents, 7022, 7023: operation buttons, 7024: connection terminal, 7025: watchband, 7026: microphone, 7029: sensor, 7030: speakers, 7052, 7053, 7054: information, 9310: portable information terminal, 9311: display portion, 9312: display region, 9313: hinge portion, 9315: a housing.

Claims (16)

1. A compound represented by formula (G1):
Figure FDA0002659073450000011
wherein A represents one of a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms and a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms,
R1represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms,
and, Y1And Y2Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms.
2. A compound according to claim 1, which is a pharmaceutically acceptable salt thereof,
wherein R is1Represents an aryl group having 6 to 25 carbon atoms,
the aryl group having a first substituent and a second substituent,
and the first substituent and the second substituent each represent any of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a cycloalkyl group having 7 to 10 carbon atoms and having a crosslinked structure.
3. A compound according to claim 1, which is a pharmaceutically acceptable salt thereof,
wherein the compound is represented by formula (G2):
Figure FDA0002659073450000021
a represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms,
R1to R3Each independently represents a substituted or unsubstituted aryl group having 6 to 25 carbon atoms,
And Y is1And Y2Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms.
4. A compound according to claim 1, which is a pharmaceutically acceptable salt thereof,
wherein the compound is represented by formula (G3):
Figure FDA0002659073450000031
a represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms,
Z1to Z3Each independently has a structure represented by any one of the formulae (Z-1), (Z-2) and (Z-3),
X1and X2Each independently represents an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms12 is any one of a trialkyl silyl group,
Y1to Y4Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms,
Ar1and Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms,
and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3And Y4Any one of the same substituents as in (1).
5. A compound according to claim 1, which is a pharmaceutically acceptable salt thereof,
wherein the compound is represented by formula (G4):
Figure FDA0002659073450000051
a represents a substituted or unsubstituted fused aromatic ring having 10 to 30 carbon atoms or a substituted or unsubstituted fused heteroaromatic ring having 10 to 30 carbon atoms,
Z1And Z2Each independently has a structure represented by any one of the formulae (Z-4), (Z-5) and (Z-6),
X1and X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms,
Y1to Y6Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms,
Ar1and Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms,
and Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3、Y4、Y5And Y6Any one of the same substituents as in (1)。
6. A compound according to claim 1, which is a pharmaceutically acceptable salt thereof,
wherein the compound is represented by formula (G5):
Figure FDA0002659073450000061
Z1to Z3Each independently has a structure represented by any one of the formulae (Z-1), (Z-2) and (Z-3),
X1and X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms,
Y1to Y4Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms,
Ar1and Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms,
Ar1And Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3And Y4Any one of the same substituent as in (1),
and R is4To R11Each independently represents any one of hydrogen, an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 25 carbon atoms.
7. A compound according to claim 1, which is a pharmaceutically acceptable salt thereof,
wherein the compound is represented by formula (G6):
Figure FDA0002659073450000081
Z1and Z2Each independently has a structure represented by any one of the formulae (Z-4), (Z-5) and (Z-6),
X1and X2Each independently represents any one of an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, and a trialkylsilyl group having 3 to 12 carbon atoms,
Y1to Y6Each independently represents a cycloalkyl group having a crosslinking structure and having 7 to 10 carbon atoms,
Ar1and Ar2Each independently represents a substituted or unsubstituted aromatic hydrocarbon having 6 to 13 carbon atoms,
Ar1and Ar2Has a chemical bond with X1、X2、Y1、Y2、Y3、Y4、Y5And Y6Any one of the same substituent as in (1),
and R is4To R11Each independently represents any one of hydrogen, an alkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a trialkylsilyl group having 3 to 12 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 25 carbon atoms.
8. A compound according to claim 1, which is a pharmaceutically acceptable salt thereof,
wherein the compound is represented by formula (100):
Figure FDA0002659073450000101
9. a light emitting device comprising the compound of claim 1.
10. A light emitting device comprising an EL layer between a pair of electrodes,
wherein the EL layer comprises the compound of claim 1.
11. A light emitting device comprising an EL layer between a pair of electrodes,
wherein the EL layer includes a light-emitting layer,
and the light-emitting layer comprises the compound of claim 1.
12. The light-emitting device as set forth in claim 11,
wherein the light emitting layer further comprises a phosphorescent material.
13. The light-emitting device as set forth in claim 11,
wherein the luminescent layer further comprises a TADF material.
14. A light emitting device comprising:
the light emitting device of claim 11; and
at least one of a transistor and a substrate.
15. An electronic device, comprising:
the light-emitting device according to claim 14; and
at least one of a microphone, a camera, an operation button, an external connection portion, and a speaker.
16. An illumination device, comprising:
the light emitting device of claim 9; and
at least one of a housing, a cover, and a support table.
CN202010898337.4A 2019-08-29 2020-08-31 Compound, light-emitting device, light-emitting apparatus, electronic device, and lighting apparatus Pending CN112441930A (en)

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US4188401A (en) 1977-06-04 1980-02-12 Bayer Aktiengesellschaft Combating fungi with 1-(ω-substituted pentyl)-3-(2-cyano-acetyl)-ureas
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EP0765106B1 (en) 1995-09-25 2002-11-27 Toyo Ink Manufacturing Co., Ltd. Light-emitting material for organic electroluminescence device, and organic electroluminescence device for which the light-emitting material is adapted
DE19803889A1 (en) 1998-01-31 1999-08-05 Bosch Gmbh Robert Electroluminescent arrangement using doped blend systems
CN101068041B (en) * 2002-07-19 2010-08-18 出光兴产株式会社 Organic electroluminescent device and organic light-emitting medium
TWI638472B (en) 2012-08-03 2018-10-11 日商半導體能源研究所股份有限公司 Light-emitting element
WO2014025114A1 (en) * 2012-08-10 2014-02-13 주식회사 두산 Organic light-emitting compound and organic electroluminescent device using same
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KR20160119047A (en) * 2014-01-31 2016-10-12 이데미쓰 고산 가부시키가이샤 Compound, material for organic electroluminescent elements, organic electroluminescent element and electronic device
KR102353663B1 (en) * 2016-05-20 2022-01-19 가부시키가이샤 한도오따이 에네루기 켄큐쇼 Light-emitting element, light-emitting device, electronic device, and lighting device
US11038111B2 (en) * 2017-11-28 2021-06-15 Samsung Display Co., Ltd. Organic electroluminescence device and monoamine compound for organic electroluminescence device
US20210206767A1 (en) * 2019-12-27 2021-07-08 Semiconductor Energy Laboratory Co., Ltd. Compound, light-emitting device, light-emitting apparatus, electronic device, and lighting device
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